DOI: 10.1002/ejoc.201600684 Full Paper

Organofluorine Chemistry

Complementary Methods for the Introduction of the (E)-3-(Pentafluorosulfanyl)allyl Chain unto O-, N-, S-, and C-BasedNucleophilesJustine Desroches,[a][‡] Elsa Forcellini,[a][‡] and and Jean-François Paquin*[a]

Abstract: Two methods for the introduction of the (E)-3-(pentafluorosulfanyl)allyl chain unto various nucleophiles wereinvestigated: a palladium-catalyzed Tsuji–Trost reaction of (E)-ethyl [3-(pentafluorosulfanyl)allyl]carbonate and a nucleophilicsubstitution reaction on (E)-[3-(pentafluorosulfanyl)allyl] 4-methylbenzenesulfonate. Various nucleophiles were examinedincluding phenols, aliphatic and aromatic amines, aliphatic and

IntroductionThe introduction of a fluorinated substituent into a molecule isa common approach to modulate its physicochemical proper-ties or its biological activity.[1] In particular, a 4,4,4-trifluorobut-2-ene chain attached to a heteroatom (mostly a phenolic oxy-gen, i.e., 1, X = O, R = Ar in Figure 1) has been reported asa beneficial fluorinated substituent in various fields includingmedicinal chemistry,[2] agrochemistry,[3] and material scien-ces.[4] We have recently described reaction conditions allowing

Figure 1. The (E)-3-(pentafluorosulfanyl)allyl chain as a potentially valuableSF5-containing substituent.

[a] CCVC, PROTEO, Département de Chimie, Université Laval,1045 avenue de la Médecine, Québec, Québec, G1V 0A6 CanadaE-mail: jean-francois.paquin@chm.ulaval.cahttp://www.chm.ulaval.ca/jfpaquin/

[‡] These authors contributed equally to this work.Supporting information for this article is available on the WWW underhttp://dx.doi.org/10.1002/ejoc.201600684.

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aromatic thiols and malonates. Overall, the two approacheswere found to be complementary as the Tsuji–Trost reactionworked better with phenols while the SN2 reaction generallyprovided better results with the amines. In addition, the sulfur-based product could only be obtained using the SN2 reactionwhile the malonates only worked under the Tsuji–Trost condi-tions.

the synthesis of such compounds, but also extending the reac-tion to nucleophiles other than phenols (e.g., amines, thiols andmalonates).[5,6]

The SF5 substituent was first reported in 1950.[7] This grouphas distinctive properties and is also referred to as a “superCF3“. Indeed, it is more electron-withdrawing, more lipophilic,more chemically/metabolically stable, and induces a strongerdipole moment than CF3.[8–10] The SF5 substituent is alsoslightly larger than a CF3, but smaller than a tBu because ofits slightly distorted square-based pyramidal geometry.[8] Theseunique properties have made the pentafluorosulfanyl group,the “substituent of the future”,[11] and it has found applicationsin various fields including material sciences,[12] agrochemis-try,[13] and medicinal chemistry.[14]

In this context, we envisioned that the (E)-3-(penta-fluorosulfanyl)allyl chain could potentially represent a valuablefluorinated substituent for medicinal chemistry, agrochemistryand material sciences (Figure 1). To the best of our knowledge,there is only one reported example of a molecule bearing the(E)-3-(pentafluorosulfanyl)allyl chain, a pentafluorosulfanylatedpeptide.[15]

Herein, we report two approaches for the introduction of the(E)-3-(pentafluorosulfanyl)allyl chain (Figure 2): the palladium-catalyzed Tsuji–Trost reaction of (E)-ethyl [3-(pentafluorosulf-anyl)allyl]carbonate (2a) and the nucleophilic substitution reac-tion of (E)-[3-(pentafluorosulfanyl)allyl] 4-methylbenzenesulfon-ate (2b). Various nucleophiles were investigated includingphenols, aliphatic and aromatic amines, aliphatic and aromaticthiols and malonates. The two approaches were found to becomplementary as the Tsuji–Trost reaction worked better withphenols while the SN2 reaction generally provided better resultswith the amines. In addition, the sulfur-based product couldonly be obtained using the SN2 reaction while the malonatesonly worked under the Tsuji–Trost conditions. Overall, not only

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these transformations provide practical methods for the intro-duction of the (E)-3-(pentafluorosulfanyl)allyl chain, but theyalso document a new reactivity pattern for molecules contain-ing a vinylic pentafluorosulfanyl group, a sub-group of SF5-con-taining compounds scarcely studied in the literature.[8c]

Figure 2. Complementary approaches reported in this study.

Results and DiscussionWe initially set up to find optimized conditions for both trans-formations. For that purpose and inspired by our recent workon the introduction of the 4,4,4-trifluorobut-2-ene chain,[5,6]

carbonate 2a and tosylate 2b[16] were chosen as the partnerfor the Tsuji–Trost reaction and the nucleophilic substitutionreaction respectively. As shown in Scheme 1, both could beprepared in one step from commercially available (3-hydroxy-1-propenyl)sulfur pentafluoride (7).[17,18]

Scheme 1. Synthesis of the SF5-containing precursors 2a and 2b from 7.

The Tsuji–Trost reaction was first optimized. Surprisingly, noreaction was observed under the conditions used for the tri-fluoromethyl analogue.[5] As such, other conditions were ex-plored using 2a with phenol as the nucleophile at 50 °C for 18 hand selected results are shown in Table 1. First, using 5 mol-%of Pd(PPh3)4 in THF provided the desired product in 60 % NMRyield (Table 1, entry 1). Addition 1 equiv. of an inorganic base,Cs2CO3, increased the yield to 72 % (Table 1, entry 2). When anorganic base, triethylamine, was used instead, a poor yield(24 %) was obtained (Table 1, entry 3). Either increase (Table 1,entry 4) or decrease (Table 1, entry 5) the amount of Cs2CO3

resulted in lower yield. Changing the catalyst system to a com-bination of Pd2dba3 (5 mol-%) and PPh3 (20 mol-%) providedan identical yield (Table 1, entry 6) than with 5 mol-% ofPd(PPh3)4. Since Pd2dba3 is less air-sensitive than Pd(PPh3)4, itwas used for the rest of the optimization. A slight increase inyield was obtained by switching from Cs2CO3 to K2CO3, so thelatter was utilized for the remainder of the optimization. Arange of ligand was then screened. Almost no product was ob-

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tained when using PCy3 (Table 1, entry 8) whereas moderateyields (55–70 %) were obtained with dppf, dppp or 1,10-phen-anthroline (phen) Table 1, (entries 9–11). The best yield wasobtained when rac-BINAP was used as the ligand (Table 1, entry12). Finally, the effect of the solvent when using rac-BINAP asthe ligand was investigated. Using CH3CN, DMF or toluene allprovided lower yields (Table 1, entries 13–15) while using amixture of THF/H2O (2:1) had no effect on the yield (Table 1,entry 16). The conditions shown in entry 12 were chosen as theoptimized ones for the Tsuji–Trost reaction. To the best of ourknowledge, this represents the first successful example of aTsuji–Trost reaction on a substrate containing a vinylic penta-fluorosulfanyl group.

Table 1. Selected optimization results for the Tsuji–Trost reaction of 2a.[a]

Entry [Pd cat.] Ligand (mol-%) Base Solvent Yield[equiv.] [%][b]

1 Pd(PPh3)4 – – THF 602 Pd(PPh3)4 – Cs2CO3 (1) THF 723 Pd(PPh3)4 – Et3N (1) THF 244 Pd(PPh3)4 – Cs2CO3 (2) THF 375 Pd(PPh3)4 – Cs2CO3 (0.5) THF 566 Pd2dba3 PPh3 (20) Cs2CO3 (1) THF 727 Pd2dba3 PPh3 (20) K2CO3 (1) THF 768 Pd2dba3 PCy3 (20) K2CO3 (1) THF 69 Pd2dba3 dppf (10) K2CO3 (1) THF 5510 Pd2dba3 dppp (10) K2CO3 (1) THF 6111 Pd2dba3 phen (10)[c] K2CO3 (1) THF 7012 Pd2dba3 rac-BINAP (10) K2CO3 (1) THF 82[d]

13 Pd2dba3 rac-BINAP (10) K2CO3 (1) CH3CN 5714 Pd2dba3 rac-BINAP (10) K2CO3 (1) DMF 2315 Pd2dba3 rac-BINAP (10) K2CO3 (1) toluene 1416 Pd2dba3 rac-BINAP (10) K2CO3 (1) THF/H2O (2:1) 80

[a] Reaction conditions: 2a (0.117 mmol), phenol (2 equiv.), Pd cat. (5 mol-%), ligand, K2CO3, base, solvent (0.4 M), 50 °C, 18 h. The optimal conditionsare in bold. [b] Yield determined by NMR analysis of the crude mixture using2-fluoro-4-nitrotoluene as an internal standard. [c] phen = 1,10-phenanthrol-ine. [d] Isolated yield.

In parallel, we explored the use of the nucleophilic substitu-tion reaction of 2b. The optimization was performed this timeusing 4-phenylphenol as the nucleophile for a reaction time of20 h (Table 2). When using the conditions developed for (E)-4,4,4-trifluorobut-2-en-1-yl 4-methylbenzenesulfonate,[6] the de-sired compound 3b was isolated in 22 % yield (Table 2, entry1). Using the preformed sodium phenolate instead resulted ina low 10 % yield (Table 2, entry 2). Increasing the amount ofthe phenol to 4 equiv. resulted in a moderate 56 % yield(Table 2, entries 3–4). Changing K2CO3 for iPr2EtN or KHCO3

provided lower yields (Table 2, entries 5–6) although a moder-ate NMR yield of 72 % was obtained if 3 equiv. of KHCO3 insteadof 1 equiv. were used (Table 2, entry 7). At this point, while theconditions developed provided a reasonable yield, the amountof phenol and base was deemed too high. The optimizationwas further pursued by investigating other solvents using

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1.1 equiv. of the phenol with 1 equiv. of K2CO3. While THF pro-vided 19 % NMR yield (Table 2, entry 8), the use of DMF andDMSO gave lower yield (Table 2, entries 9–10). The use of tolu-ene gave a promising 41 % NMR yield (Table 2, entry 11) andincreasing the temperature to 100 °C provided 3b in 70 % NMRyield. Finally, increasing the amount of phenol to 2 equiv. gave3b in 84 % isolated yield. The conditions shown in entry 14were chosen as the optimized ones for the nucleophilic substi-tution reaction.

With both reaction conditions optimized, we then evaluatedthe scope in a comparative manner using phenols (Scheme 2),amines (Scheme 3), thiols (Scheme 4), and malonates(Scheme 5) as nucleophiles.[19]

For the phenols (Scheme 2), the yields obtained using theTsuji–Trost conditions were found to be, with a few exceptions,superior to the ones obtained from the nucleophilic substitu-tion reaction. For instance, using phenol as the nucleophile, theproduct 3a was obtained in 82 % using the Tsuji–Trost condi-tions in comparison to 68 % for the nucleophilic substitutionreactions. While in most cases, the difference was small (i.e., lessthan 10 %), in some occasions, the difference in yields in favourof the Tsuji–Trost conditions was important (e.g., 3a, 3e, 3j, 3k,3l, 3m and 3n). Nevertheless, phenol bearing single substitu-ents in para, meta or ortho positions could be used. Notably,the presence of a bromide or chloride (e.g., 3f, 3h, 3i or 3l)was well tolerated opening the door for further metal-catalyzedtransformations of the product obtained. The presence of astrong electron-withdrawing substituent such as a nitro groupwas problematic, and the resulting product was only obtained

Scheme 2. Scope with phenol nucleophiles. [a] The reaction was conducted at 80 °C. [b] Estimated by NMR analysis of the crude mixture.

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Table 2. Selected optimization results for the substitution reaction of 2b.[a]

Entry ArOH Base Solvent Temp Yield[equiv.][b] [equiv.] [°C] [%][c]

1 1.1 K2CO3 (1) CH3CN 60 22[d]

2[e] 1.1 – CH3CN 60 10[d]

3 2 K2CO3 (1) CH3CN 60 35[d]

4 4 K2CO3 (1) CH3CN 60 565 4 iPr2EtN (1) CH3CN 60 366 4 KHCO3 (1) CH3CN 60 27[d]

7 4 KHCO3 (3) CH3CN 60 728 1.1 K2CO3 (1) THF 60 199 1.1 K2CO3 (1) DMF 60 510 1.1 K2CO3 (1) DMSO 60 611 1.1 K2CO3 (1) toluene 60 4112 1.1 K2CO3 (1) toluene 80 6313 1.1 K2CO3 (1) toluene 100 7014 2 K2CO3 (1) toluene 100 84[d]

[a] Reaction conditions: 2b (0.15 mmol), 4-phenylphenol, base, solvent(0.25 M), heat, 20 h. The optimal conditions are in bold. [b] Ar = 4-Ph-C6H4.[c] Yield determined by NMR analysis of the crude mixture using 2-fluoro-4-nitrotoluene as an internal standard. [d] Isolated yield. [e] Sodium 4-phenyl-phenolate was used instead of 4-phenylphenol.

in low yield through the Tsuji–Trost protocol. We assume thatthis is due to the low nucleophilicity of the phenoxide gener-ated under the conditions. Functionalized phenols such as va-

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Scheme 3. Scope with amine nucleophiles. [a] Et3N (1 equiv.) was added as the hydrochloride salt of the amine was used.

Scheme 4. Reaction with thiol nucleophiles.

Scheme 5. Reaction with malonates.

nillin, eugenol or estrone could be used with both protocolsalthough the yields of the products 3j, 3k and 3n were signifi-

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cantly better with the Tsuji–Trost reaction (76–80 %) than thesubstitution reaction (13–40 %).

The scope of the reaction using amines is shown inScheme 3. In this case, and with the exception of aniline deriva-tives, the nucleophilic substitution reaction provided systemati-cally better yields than the Tsuji–Trost reaction (6–32 % higher).Secondary aliphatic amines including a chiral one could beused and the products were obtained in moderate to goodyields (up to 83 % yield for 4c using the nucleophilic substitu-tion reaction conditions). Secondary allylic or benzylic aminederivatives could also be utilized and moderate to good yieldsof the products 4d–g could be achieved. Notably, using N-benzyl-N-ethanolamine as the nucleophile, only the product ofN-alkylation (4g) was isolated.[19] The Tsuji–Trost conditionscould not be used for primary amines as complex mixtureswere always observed. This behavior was also observed whentrying to install the 4,4,4-trifluorobut-2-ene chain.[5] However,good yields (77–86 %) of the desired products 4h–j could beobtained using the nucleophilic substitution reaction condi-tions. Finally, aniline derivatives could also be employed asnucleophiles although in the case, yields of the products waseither identical (4m) or substantially higher (45–57 % for 4n–o)under the Tsuji–Trost conditions.

The reaction with thiols was next investigated (Scheme 4).Under the Tsuji–Trost conditions, no conversion was observedwith either an aliphatic or an aromatic thiol. We hypothesizethat it was due to catalyst poisoning.[5] The use of the nucleo-philic substitution conditions on 2b, however, provided the de-sired products. Hence, using an alkylthiol, e.g., 1-dodecanethiol,provided the allylic sulfide 5a in 79 % yield whereas using anaromatic thiol, e.g., thiophenol, gave product 5b in 76 % NMR

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yield. In this particular case, it was difficult to remove the excessthiol by flash chromatography. Nonetheless, 24 % of pure 5bcould be obtained.

Finally, reaction of 2a and 2b with malonates was explored.Surprisingly, no or low conversion was observed using 2b undernucleophilic substitution conditions. This contrasts drastically tothe results obtained previously with (E)-4,4,4-trifluorobut-2-en-1-yl 4-methylbenzenesulfonate.[6] Hence, we focused on the useof the Tsuji–Trost conditions with 2a. Using dibenzylmalo-nate,[20] a mixture of the desired product (6a) and dialkylatedmalonate 8 were observed by NMR in the crude reaction mix-ture (ratio 6a/8 = 21:79) and product 8 was isolated in 71 %yield. Using monosubstituted malonates (e.g., dibenzyl 2-meth-ylmalonate or dibenzyl 2-benzylmalonate) instead resulted inmoderate yields of the expected products 6b and 6c. In thosecases, the number of equivalent of the nucleophile had to bereduced to 1 equiv. in order to facilitate the purification, whichmay explain the lower yields observed.

Conclusions

We have described two methods for the introduction of the(E)-3-(pentafluorosulfanyl)allyl chain, a potentially valuable SF5-containing substituent, unto various nucleophiles: a palladium-catalyzed Tsuji–Trost reaction of (E)-ethyl [3-(pentafluoro-sulfanyl)allyl]carbonate and a nucleophilic substitution reactionon (E)-[3-(pentafluorosulfanyl)allyl] 4-methylbenzensulfonate.Various nucleophiles were examined including phenols, ali-phatic and aromatic amines, aliphatic and aromatic thiols andmalonates. Overall, the two approaches were found to be com-plementary as the Tsuji–Trost reaction worked better withphenols while the SN2 reaction generally provided better resultswith the amines. In addition, the sulfur-based product couldonly be obtained using the SN2 reaction while the malonatesonly reacted under the Tsuji–Trost conditions. Further synthetictransformations of the products generated throughout thisstudy are underway and will be reported in due course.

Experimental SectionGeneral Information: The following includes general experimentalprocedures, specific details for representative reactions, and isola-tion and spectroscopic information for the new compounds pre-pared. Preparation of the substrates 2 and nucleophilic substitutionreactions were carried out under an argon atmosphere with drysolvents. Et2O, CH3CN and toluene were purified using a VacuumAtmospheres Inc. Solvent Purification System. The use of dry THFwas not necessary for the Tsuji–Trost reaction. All other commer-cially available compounds were used as received. Thin-layer chro-matography (TLC) analysis of reaction mixtures was performed us-ing Silicycle silica gel 60 Å F254 TLC plates, and visualized underUV or by staining with either potassium permanganate or phospho-molybdic acid. Flash column chromatography was carried out onSilicycle silica gel 60 Å, 230–400 mesh. 1H, 13C and 19F NMR spectrawere recorded in CDCl3 at ambient temperature using Agilent DD2500 and Varian Inova 400 spectrometers. Coupling constants areexpressed in Hz and the abbreviations used for multiplicity are asfollows: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet,

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h = sextet, m = multiplet, br = broad resonance. 1H and 13C NMRchemical shifts are reported in ppm downfield of tetramethylsilaneand are respectively referenced to residual solvent (δ = 7.26 and77.16 ppm for CDCl3). For 19F NMR, CFCl3 is used as the externalstandard. High-resolution mass spectra were obtained on a LC/MS-TOF Agilent 6210 using electrospray ionization (ESI) or atmosphericpressure photoionization (APPI). Infrared spectra were recorded us-ing a Thermo Scientific Nicolet 380 FT-IR spectrometer. Meltingpoints were recorded on a Stanford Research System OptiMelt capil-lary melting point apparatus. Dibenzyl 2-methylmalonate and di-benzyl 2-benzylmalonate were prepared following known proto-cols.[5,21]

(E)-Ethyl [3-(Pentafluorosulfanyl)allyl]carbonate (2a): To a solu-tion of (3-hydroxy-1-propenyl)sulfur pentafluoride (200 mg,1.08 mmol) in anhydrous diethyl ether (4 mL) and under argonatmosphere were added successively pyridine (351 μL, 4.34 mmol,4 equiv.), 4-(dimethylamino)pyridine (26 mg, 0.29 mmol, 0.2 equiv.)and ethyl chloroformate (622 μL, 6.48 mmol, 6 equiv.). The reactionmixture was stirred at room temperature and under argon atmos-phere for 72 h. Water was then added and the aqueous phase wasextracted 3 times with diethyl ether. The organic phase was thenwashed with brine, dried with MgSO4, filtered and the solvent wasremoved by a distillation at atmospheric pressure using a Vigreuxcolumn. The crude product was purified by column chromatogra-phy (eluent: 90:10 pentane/Et2O) affording the title compound afterdistillation using a Vigreux column (193 mg, 70 %) as a colourlessoil. IR (ATR, ZnSe): ν̃ = 3095, 2990, 1750, 1253, 895, 826, 789, 765cm–1. 1H NMR (500 MHz, CDCl3): δ = 6.70 (dpt, J = 14.7, 6.3, 2.0 Hz,1 H), 6.55 (dtp, J = 14.7, 4.5, 1.2 Hz, 1 H), 4.78 (dh, J = 4.3, 2.1 Hz, 2H), 4.25 (q, J = 7.1 Hz, 2 H), 1.33 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR(126 MHz, CDCl3): δ = 154.5, 142.1 (p, J = 21.6 Hz), 132.1 (p, J =7.2 Hz), 65.0, 63.8, 14.3 ppm. 19F NMR (470 MHz, CDCl3): δ = 82.9–81.6 (m, 1 F), 62.9 (dd, J = 150.8, 6.2 Hz, 4 F) ppm. HRMS APPI calcd.for C6H9F5O3S [M*]+ 257.0265 found 257.0275.

(E)-[3-(Pentafluorosulfanyl)allyl] 4-Methylbenzenesulfonate(2b): To a solution of (3-hydroxy-1-propenyl)sulfur pentafluoride(1.5 g, 8.15 mmol) in anhydrous diethyl ether (18 mL) under argonatmosphere were added successively triethylamine (1.14 mL,8.15 mmol, 1 equiv.), 4-(dimethylamino)pyridine (100 mg,0.815 mmol, 0.1 equiv.) and tosyl chloride (1.55 g, 8.15 mmol,1 equiv.). The reaction mixture was stirred at room temperatureunder argon atmosphere for 72 h. Water was then added and theaqueous phase was extracted with diethyl ether 3 times. The or-ganic phases were combined, washed with 3 N HCl, NaHCO3, andbrine. They were then dried with MgSO4 and the solvent was evapo-rated under reduced pressure. The crude product was then purifiedby column chromatography (eluent: 60:35:5 hexane/dichloro-methane/diethyl ether) to afford 2b as an off-white solid (1.86 g,68 %), m.p. 56–57 °C. IR (ATR, ZnSe): ν̃ = 3103, 2941, 1363, 1175,901, 802, 726 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.83–7.78 (m, 2H), 7.40–7.35 (m, 2 H), 6.61 (dpt, J = 14.5, 6.3, 2.0 Hz, 1 H), 6.41 (dtp,J = 14.7, 4.5, 1.2 Hz, 1 H), 4.67 (dh, J = 4.3, 2.1 Hz, 2 H), 2.46 (s, 3 H)ppm. 13C NMR (126 MHz, CDCl3): δ = 145.8, 142.7 (p, J = 21.3 Hz),132.4, 130.8 (p, J = 7.0 Hz), 130.3, 128.1, 65.7, 21.8 ppm. 19F NMR(470 MHz, CDCl3): δ = 82.3–80.8 (m, 1 F), 62.9 (dd, J = 151.4, 6.2 Hz,4 F) ppm. HRMS ESI+ calcd. for C10H11F5O3S2 [M + NH4]+ 356.0414found 356.0414.

General Procedure for the Tsuji–Trost Reaction Using 2a: In asealable vial, to a solution of (E)-ethyl [3-(pentafluorosulfanyl)allyl]carbonate 2a (30 mg, 0.117 mmol) in THF (0.3 mL) were successfullyadded the nucleophile (0.234 mmol, 2 equiv.), K2CO3 (16 mg,0.117 mmol, 1 equiv.), rac-BINAP (7.5 mg, 0.012 mmol, 10 mol-%),

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Pd2dba3 (5.4 mg, 0.006 mmol, 5 mol-%). The vial vas sealed and thereaction mixture was stirred at 50 °C for 18 h. After cooling to roomtemperature, water was added and the aqueous phase was ex-tracted 3 times with diethyl ether. The organic phases were com-bined, washed with brine, dried with MgSO4 and the solvent wasevaporated. The crude product was purified by column chromatog-raphy to yield the desired compound.

General Procedure for the Nucleophilic Substitution Using 2b:To a sealable vial under argon atmosphere were successivelycharged, the nucleophile (0.30 mmol, 2 equiv.), K2CO3 (0.15 mmol,1 equiv.) and dry toluene (0.3 mL). The resulting mixture was heatedfor 2 min at 100 °C in a preheated oil bath before addition of (E)-3-(pentafluorosulfanyl)allyl 4-methylbenzenesulfonate 2b (0.15 mmol,1 equiv.) diluted in dry toluene (0.3 mL). The mixture was heatedat 100 °C for 20 h. Water was then added to quench the reactionand the mixture was extracted with Et2O. The organic layers werecombined and washed with brine, dried with MgSO4 and concen-trated under reduced pressure. The crude product was purified byflash chromatography on silica gel.

(E)-Pentafluoro(3-phenoxyprop-1-en-1-yl)sulfane (3a): Followingthe general Tsuji–Trost procedure, 3a was isolated as a colourlessoil (25 mg, 82 %) after purification by flash chromatography usingpentane/Et2O (95:5) as the eluent. Following the general nucleo-philic substitution procedure, 3a was isolated as a colourless oil(26 mg, 68 %) after purification by flash chromatography using hex-ane/Et2O (90:10) as the eluent. IR (ATR, ZnSe): ν̃ = 3065, 2935, 1496,1240, 905, 836, 748, 690 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.39–7.28 (m, 2 H), 7.07–6.98 (m, 1 H), 6.96–6.76 (m, 3 H), 6.73–6.61 (m,1 H), 4.69 (dh, J = 4.7, 2.3 Hz, 2 H) ppm. 13C NMR (126 MHz, CDCl3):δ = 157.7, 141.6 (p, J = 20.8 Hz), 133.8 (p, J = 6.9 Hz), 129.9, 122.0,114.7, 64.8 ppm. 19F NMR (470 MHz, CDCl3): δ = 89.4–69.7 (m, 1 F),63.2 (dd, J = 150, 6.3 Hz) ppm. HRMS APPI calcd. for C9H9F5OS [M*]+

260.0294 found 260.0289.

(E)-{3-[(1,1′-Biphenyl)-4-yloxy]prop-1-en-1-yl}pentafluoro-sulfane (3b): Following the general Tsuji–Trost procedure, 3b wasisolated as a white solid (32 mg, 81 %) after purification by flashchromatography using hexane/CH2Cl2 (95:5) as the eluent. Follow-ing the general nucleophilic substitution procedure, 3b was isolatedas a white solid (42 mg, 84 %) after purification by flash chromatog-raphy using hexane/Et2O (95:5) as the eluent, m.p. 125–126 °C. IR(ATR, ZnSe): ν̃ = 2902, 1605, 1489, 1248, 1024, 905, 823, 759 cm–1.1H NMR (500 MHz, CDCl3): δ = 7.59–7.51 (m, 4 H), 7.47–7.41 (m, 2H), 7.36–7.31 (m, 1 H), 7.02–6.96 (m, 2 H), 6.87 (dpt, J = 14.6, 6.4,2.2 Hz, 1 H), 6.70 (dtp, J = 14.6, 3.9, 1.2 Hz, 1 H), 4.73 (dh, J = 4.4,2.2 Hz, 2 H) ppm. 13C NMR (126 MHz, CDCl3): δ = 157.3, 141.7 (p,J = 21.3 Hz), 140.6, 135.1, 133.7 (p, J = 7.1 Hz), 128.9, 128.5, 127.1,126.9, 115.1, 65.0 ppm. 19F NMR (470 MHz, CDCl3): δ = 83.7–82.4(m, 1 F), 63.2 (dd, J = 151.2, 6.2 Hz, 4 F) ppm. HRMS APPI calcd. forC15H13F5OS [M*]+ 336.0602 found 336.0601.

(E)-{3-[4-(tert-Butyl)phenoxy]prop-1-en-1-yl}pentafluorosulf-ane (3c): Following the general Tsuji–Trost procedure, 3c was iso-lated as a white solid (28 mg, 77 %) after purification by flash chro-matography using hexane/Et2O (95:5) as the eluent. Following thegeneral nucleophilic substitution procedure, 3c was isolated as awhite solid (34 mg, 72 %) after purification by flash chromatographyusing hexane/Et2O (95:5) as the eluent, m.p. 50–51 °C. IR (ATR,ZnSe): ν̃ = 2962, 1511, 1237, 1188, 914, 835, 752, 697 cm–1. 1H NMR(500 MHz, CDCl3): δ = 7.33 (m, 2 H), 6.85 (m, 2 H), 6.88–6.79 (m, 1H), 6.67 (dtp, J = 14.6, 3.8, 1.2 Hz, 1 H), 4.67 (dh, J = 3.8, 2.3 Hz, 2H), 1.31 (s, 9 H) ppm. 13C NMR (126 MHz, CDCl3): δ = 155.6, 14.8,141.5 (p, J = 20.9 Hz), 134.0 (p, J = 7.1 Hz), 126.6, 114.3, 65.0, 34.3,31.6 ppm. 19F NMR (470 MHz, CDCl3): δ = 83.8–82.5 (m, 1 F), 63.2

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(dd, J = 150.2, 6.2 Hz, 4 F) ppm. HRMS APPI calcd. for C13H17F5OS[M*]+ 316.0915 found 316.0916.

(E)-Pentafluoro[3-(4-methoxyphenoxy)prop-1-en-1-yl]sulfane(3d): Following the general Tsuji–Trost procedure, 3d was isolatedas an off-white white solid (26 mg, 76 %) after purification by flashchromatography using hexane/Et2O (90:10) as the eluent. Followingthe general nucleophilic substitution procedure, 3d was isolated asa white solid (29 mg, 68 %) after purification by flash chromatogra-phy using hexane/Et2O (95:5) as the eluent, m.p. 68–69 °C. IR (ATR,ZnSe): ν̃ = 3107, 2920, 1507, 1232, 1088, 1034, 824, 724 cm–1. 1HNMR (500 MHz, CDCl3): δ = 6.88–6.78 (m, 5 H), 6.66 (dtp, J = 14.6,3.9, 1.2 Hz, 1 H), 4.63 (dh, J = 4.7, 2.4 Hz, 2 H), 3.78 (s, 3 H) ppm.13C NMR (126 MHz, CDCl3): δ = 154.7, 151.9, 141.5 (p, J = 21.0 Hz),134.1 (p, J = 7.1 Hz), 115.9, 114.9, 65.8, 55.8 ppm. 19F NMR (470 MHz,CDCl3): δ = 86.2–80.7 (m, 1 F), 63.2 (dd, J = 150, 6.4 Hz) ppm. HRMSAPPI calcd. for C10H11F5O2S [M*]+ 290.0394 found 290.0393.

(E)-Pentafluoro[3-(4-nitrophenoxy)prop-1-en-1-yl]sulfane (3e):Following the general Tsuji–Trost procedure, 3e was isolated as apale yellow solid (13 mg, 36 %) after purification by flash chroma-tography using hexane/Et2O (90:10 to 80:20) as the eluent, m.p. 69–70 °C. IR (ATR, ZnSe): ν̃ = 3117, 2914, 1590, 1494, 1339, 1230, 909,801 cm–1. 1H NMR (500 MHz, CDCl3): δ = 8.27–8.23 (m, 2 H), 7.03–6.98 (m, 2 H), 6.84 (dpt, J = 14.7, 6.3, 2.1 Hz, 1 H), 6.73–6.65 (m, 1H), 4.79 (dh, J = 4.5, 2.3 Hz, 2 H) ppm. 13C NMR (126 MHz, CDCl3):δ = 162.4, 142.2 (p, J = 21.7 Hz), 132.2 (p, J = 7.0 Hz), 126.2, 114.8,65.3 ppm. 19F NMR (470 MHz, CDCl3): δ = 82.9–81.6 (m, 1 F), 63.1(dd, J = 150.6, 6.3 Hz) ppm. HRMS ESI+ calcd. for C9H8F5NO3S [M +H]+ 306.0218 found 306.0216.

(E)-[3-(4-Bromophenoxy)prop-1-en-1-yl]pentafluorosulfane(3f): Following the general Tsuji–Trost procedure, 3f was isolatedas a colourless oil (30 mg, 76 %) after purification by flash chroma-tography using hexane/Et2O (98:2) as the eluent. Following the gen-eral nucleophilic substitution procedure, 3f was isolated as a colour-less solid (34 mg, 67 %) after purification by flash chromatographyusing hexane/Et2O (99:1) as the eluent. IR (ATR, ZnSe): ν̃ = 2911,1486, 1237, 1072, 903, 813, 746 cm–1. 1H NMR (500 MHz, CDCl3):δ = 7.41 (m, 2 H), 6.86–6.77 (m, 3 H), 6.65 (dtp, J = 14.6, 3.8, 1.2 Hz,1 H), 4.66 (dh, J = 3.9, 2.3 Hz, 2 H) ppm. 13C NMR (126 MHz, CDCl3):δ = 156.8, 141.8 (p, J = 21.1 Hz), 133.3 (p, J = 7.0 Hz), 132.7, 116.5,114.3, 65.0 ppm. 19F NMR (470 MHz, CDCl3): δ = 83.5–82.2 (m, 1 F),63.1 (dd, J = 150.7, 6.4 Hz, 4 F) ppm. HRMS APPI calcd. forC9H8BrF5OS [M*]+ 337.9394found 337.9383.

(E)-Pentafluoro[3-(4-fluorophenoxy)prop-1-en-1-yl]sulfane (3g):Following the general Tsuji–Trost procedure, 3g was isolated as acolourless oil (23 mg, 82 %) after purification by flash chromatogra-phy using pentane/Et2O (95:5) as the eluent. Following the generalnucleophilic substitution procedure, 3g was isolated as a yellowoil (33 mg, 79 %) after purification by flash chromatography usinghexane/Et2O (99:1) as the eluent. IR (ATR, ZnSe): ν̃ = 3101, 2926,1505, 1207, 805, 828, 730 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.05–6.96 (m, 2 H), 6.91–6.76 (m, 3 H), 6.66 (dtp, J = 14.6, 3.9, 1.2 Hz, 1H), 4.65 (dh, J = 4.6, 2.3 Hz, 2 H) ppm. 13C NMR (126 MHz, CDCl3):δ = 158.0 (d, J = 239.5 Hz), 153.9 (d, J = 2.2 Hz), 141.7 (p, J =22.2 Hz), 133.6 (p, J = 7.0 Hz), 116.3 (d, J = 22.9 Hz), 116.0 (d, J =8.1 Hz), 65.6 ppm. 19F NMR (470 MHz, CDCl3): δ = 83.9–81.7 (m, 1F), 63.1 (dd, J = 150, 5.8 Hz, 4 F), –122.4 (tt, J = 8.3, 4.3 Hz, 1 F)ppm. HRMS APPI calcd. for C9H8F6OS [M*]+ 278.0195 found278.0199.

(E)-[3-(3-Chlorophenoxy)prop-1-en-1-yl]pentafluorosulfane(3h): Following the general Tsuji–Trost procedure, 3h was isolatedas a colourless oil (25 mg, 71 %) after purification by flash chroma-

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tography using pentane/Et2O (95:5) as the eluent. Following thegeneral nucleophilic substitution procedure, 3h was isolated as paleyellow oil (32 mg, 73 %) after purification by flash chromatographyusing pentane/Et2O (95:5) as the eluent. IR (ATR, ZnSe): ν̃ = 3104,2913, 1594, 1229, 918, 823, 755 cm–1. 1H NMR (400 MHz, CDCl3):δ = 7.24 (t, J = 8.2 Hz, 1 H), 7.01 (ddd, J = 8.0, 1.9, 0.9 Hz, 1 H), 6.93(t, J = 2.2 Hz, 1 H), 6.87–6.76 (m, 2 H), 6.66 (dtp, J = 14.7, 3.9, 1.2 Hz,1 H), 4.68 (dh, J = 4.6, 2.3 Hz, 2 H) ppm. 13C NMR (126 MHz, CDCl3):δ = 158.4, 141.8 (p, J = 21.5 Hz), 135.3, 133.1 (p, J = 7.1 Hz), 130.6,122.2, 115.3, 113.1, 65.0 ppm. 19F NMR (470 MHz, CDCl3): δ = 83.4–82.1 (m, 1 F), 63.1 (dd, J = 150.7, 6.0 Hz, 4 F) ppm. HRMS APPI calcd.for C9H8ClF5OS [M*]+ 293.9899 found 293.9897.

(E)-[3-(3-Bromophenoxy)prop-1-en-1-yl]pentafluorosulfane (3i):Following the general Tsuji–Trost procedure, 3i was isolated as acolourless oil (33 mg, 82 %) after purification by flash chromatogra-phy using hexane/Et2O (98:2) as the eluent. Following the generalnucleophilic substitution procedure, 3i was isolated as a white solid(37 mg, 74 %) after purification by flash chromatography using hex-ane/Et2O (98:2) as the eluent. IR (ATR, ZnSe): ν̃ = 3099, 2914, 1589,1474, 1227, 912, 823, 754 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.20–7.13 (m, 2 H), 7.10–7.08 (m, 1 H), 6.88–6.77 (m, 2 H), 6.69–6.62 (m,1 H), 4.67 (dh, J = 6.7, 2.5 Hz, 2 H) ppm. 13C NMR (126 MHz, CDCl3):δ = 158.4, 141.8 (p, J = 21.5 Hz), 133.1 (p, J = 7.0 Hz), 131.0, 125.1,123.1, 118.2, 113.6, 65.0. 19F NMR (470 MHz, CDCl3): δ = 83.4–82.1(m, 1 F), 63.1 (dd, J = 150.6, 6.1 Hz, 4 F). HRMS APPI calcd. forC9H8BrF5OS [M*]+ 337.9394 found 337.9396.

(E)-3-Methoxy-4-{[3-(pentafluorosulfanyl)allyl]oxy}benzalde-hyde (3j): Following the general Tsuji–Trost procedure, 3j was iso-lated as a yellow solid (29 mg, 79 %) after purification by flash chro-matography using hexane/CH2Cl2/Et2O (60:30:10) as the eluent,m.p. 68–69 °C. IR (ATR, ZnSe): ν̃ = 2850, 1677, 1585, 1238, 1134, 814,729 cm–1. 1H NMR (500 MHz, CDCl3): δ = 9.88 (s, 1 H), 7.45 (m, 2 H),6.95 (m, 1 H), 6.85 (dpt, J = 14.8, 6.3, 2.1 Hz, 1 H), 6.69 (m, 1 H), 4.83(dh, J = 4.1, 2.1 Hz, 2 H), 3.95 (s, 3 H) ppm. 13C NMR (126 MHz,CDCl3): δ = 191.0, 152.4, 150.2, 142.2 (p, J = 21.1 Hz), 132.9 (p, J =7.2 Hz), 131.3, 126.4, 112.6, 109.9, 66.0, 56.2 ppm. 19F NMR(470 MHz, CDCl3): δ = 83.2–81.9 (m, 1 F), 63.2 (dd, J = 150.6, 7.4 Hz,4 F) ppm. HRMS ESI+ calcd. for C11H11F5O3S [M + H]+ 319.0422found 319.0424.

(E)-[3-(4-Allyl-2-methoxyphenoxy)prop-1-en-1-yl]pentafluoro-sulfane (3k): Following the general Tsuji–Trost procedure, 3k wasisolated as a colourless oil (30 mg, 76 %) after purification by flashchromatography using hexane/Et2O (100:10) as the eluent. Follow-ing the general nucleophilic substitution procedure, 3k was isolatedas a yellow oil (20 mg, 40 %) after purification by flash chromatogra-phy using hexane/Et2O (98:2) as the eluent. IR (ATR, ZnSe): ν̃ = 3079,2938, 1509, 1262, 1229, 894, 829, 738 cm–1. 1H NMR (500 MHz,CDCl3): δ = 6.84 (dpt, J = 21.3, 6.5, 2.0 Hz, 1 H), 6.81 (d, J = 8.1 Hz,1 H), 6.75 (d, J = 2.0 Hz, 1 H), 6.73–6.71 (m, 1 H), 6.69–6.63 (m, 1 H),5.96 (ddt, J = 17.0, 10.3, 6.7 Hz, 1 H), 5.12–5.06 (m, 2 H), 4.71 (dh,J = 4.3, 2.2 Hz, 2 H), 3.87 (s, 3 H), 3.35 (d, J = 6.7 Hz, 1 H) ppm. 13CNMR (126 MHz, CDCl3): δ = 150.0, 145.6, 141.7 (p, J = 21.1 Hz), 137.5,135.0, 134.2 (p, J = 7.0 Hz), 120.7, 116.1, 115.3, 112.7, 67.0, 55.9, 40.0ppm. 19F NMR (470 MHz, CDCl3): δ = 83.8–82.6 (m, 1 F), 63.2 (dd,J = 150.6, 5.7 Hz, 4 F) ppm. HRMS ESI+ calcd. for C13H15F5O2S [M +H]+ 331.0786 found 331.0784.

(E)-[3-(2-Bromophenoxy)prop-1-en-1-yl]pentafluorosulfane (3l):Following the general Tsuji–Trost procedure, 3l was isolated as awhite solid (34 mg, 86 %) after purification by flash chromatographyusing hexane/Et2O (99.5:0.5) as the eluent. Following the generalnucleophilic substitution procedure, 3l was isolated as a white solid(36 mg, 71 %) after purification by flash chromatography using

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pentane/Et2O (95:5) as the eluent, m.p. 65–66 °C. IR (ATR, ZnSe): ν̃ =3101 1812, 2855, 1481, 1441, 1280, 815, 744 cm–1. 1H NMR(500 MHz, CDCl3): δ = 7.57 (dd, J = 7.9, 1.6 Hz, 1 H), 7.28 (ddd, J =8.2, 7.5, 1.6 Hz, 1 H), 6.99 (dpt, J = 14.6, 6.4, 2.3 Hz, 1 H), 6.91 (td,J = 7.7, 1.4 Hz, 1 H), 6.87 (dd, J = 8.2, 1.4 Hz, 1 H), 6.67 (dtp, J =14.6, 3.6, 1.3 Hz, 1 H), 4.76–4.72 (m, 2 H) ppm. 13C NMR (126 MHz,CDCl3): δ = 154.1, 142.0 (p, J = 21.1 Hz), 133.8, 133.1 (p, J = 7.1 Hz),128.8, 123.2, 113.7, 112.6, 65.8 ppm. 19F NMR (470 MHz, CDCl3): δ =83.9–81.5 (m, 1 F), 63.2 (dd, J = 151, 6.4 Hz) ppm. HRMS ESI+ calcd.for C9H8BrF5OS [M + K]+ 378.9010 found 378.8999.

(E)-[3-(3,5-Dimethylphenoxy)prop-1-en-1-yl]pentafluorosulfane(3m): Following the general Tsuji–Trost procedure, 3m was isolatedas a colourless solid (29 mg, 85 %) after purification by flash chro-matography using hexane/Et2O (98:2) as the eluent. Following thegeneral nucleophilic substitution procedure, 3m was isolated as anoff-white solid (29 mg, 68 %) after purification by flash chromatog-raphy using hexane/Et2O (95:5) as the eluent, m.p. 63–64 °C. IR (ATR,ZnSe): ν̃ = 3110, 2922, 1594, 1442, 1328, 1297, 937, 806 cm–1. 1HNMR (500 MHz, CDCl3): δ = 6.82 (dpt, J = 15.0, 6.4, 2.2 Hz, 1 H),6.69–6.63 (m, 2 H), 6.54 (s, 2 H), 4.65 (dh, J = 3.8, 2.3 Hz, 2 H), 2.30(s, 6 H) ppm. 13C NMR (126 MHz, CDCl3): δ = 157.8, 141.5 (p, J =21.4 Hz), 139.7, 133.7 (p, J = 7.1 Hz), 123.7, 112.5, 64.8, 21.6 ppm.19F NMR (470 MHz, CDCl3): δ = 83.5–82.6 (m, 1 F), 63.2 (dd, J =151.1, 6.1 Hz, 4 F) ppm. HRMS ESI+ calcd. for C11H13F5OS [M + H]+

289.0680 found 289.0681.

(8R,9S,13S,14S)-13-Methyl-3-{[(E)-3-(pentafluorosulfanyl)allyl]-oxy}-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopenta[a]-phenanthren-17-one (3n): Following the general Tsuji–Trost pro-cedure, 3n was isolated as an off-white solid (41 mg, 80 %) afterpurification by flash chromatography using hexane/CH2Cl2/Et2O(80:15:5) as the eluent. Following the general nucleophilic substitu-tion procedure, 3n was isolated as an off-white solid (8.4 mg, 13 %)after purification by flash chromatography using hexane/Et2O(80:20 to 60:40) as the eluent, m.p. 87–88 °C. IR (ATR, ZnSe): ν̃ =2931, 1732, 1497, 1245, 1159, 835, 766 cm–1. 1H NMR (500 MHz,CDCl3): δ = 7.23 (d, J = 8.6 Hz, 1 H), 6.82 (dpt, J = 14.8, 6.4, 2.2 Hz,1 H), 6.72 (dd, J = 8.6, 2.8 Hz, 1 H), 6.70–6.63 (m, 2 H), 4.66 (dh, J =4.4, 2.3 Hz, 1 H), 2.94–2.90 (m, 2 H), 2.51 (ddd, J = 18.9, 8.8, 0.9 Hz,1 H), 2.44–2.36 (m, 1 H), 2.31–2.22 (m, 1 H), 2.15 (dt, J = 18.9, 8.9 Hz,1 H), 2.10–1.99 (m, 2 H), 1.98–1.93 (m, 1 H), 1.68–1.35 (m, 6 H), 0.92(s, 3 H) ppm. 13C NMR (126 MHz, CDCl3): δ = 221.1, 155.8, 141.5 (p,J = 20.8 Hz), 138.3, 134.0 (p, J = 7.0 Hz), 133.4, 126.7, 115.0, 112.2,64.9, 50.5, 48.1, 44.1, 38.4, 36.0, 31.7, 29.8, 26.6, 26.0, 21.7, 14.0 ppm.19F NMR (470 MHz, CDCl3): δ = 83.9–82.5 (m, 1 F), 63.2 (dd, J =150.7, 6.2 Hz, 4 F) ppm. HRMS ESI+ calcd. for C21H25F5O2S [M + H]+

437.1568 found 437.1572.

(E)-4-[3-(Pentafluorosulfanyl)allyl]morpholine (4a): Followingthe general Tsuji–Trost procedure, 4a was isolated as a yellow oil(17 mg, 58 %) after purification by flash chromatography usingpentane/Et2O (50:50) as the eluent. Following the general nucleo-philic substitution procedure, 4a was isolated as a yellow oil (24 mg,64 %) after purification by flash chromatography using pentane/Et2O (50:50) as the eluent. IR (ATR, ZnSe): ν̃ = 2918, 2855, 2814,1455, 1296, 1116, 828, 725 cm–1. 1H NMR (500 MHz, CDCl3): δ =6.61 (dpt, J = 12.6, 6.3, 1.6 Hz, 1 H), 6.49 (dtp, J = 14.5, 6.0, 1.2 Hz,1 H), 3.72 (t, J = 4.6 Hz, 4 H), 3.11 (dh, J = 5.8, 2.0 Hz, 2 H), 2.46 (d,J = 4.6 Hz, 4 H) ppm. 13C NMR (126 MHz, CDCl3): δ = 142.5 (p, J =19.7 Hz), 135.5 (p, J = 7.0 Hz), 67.0, 57.9, 53.7 ppm. 19F NMR(470 MHz, CDCl3): δ = 84.0–82.7 (m, 1 F), 62.9 (dd, J = 151, 6.3 Hz,4 F) ppm. HRMS ESI+ calcd. for C7H13F5NOS [M + H]+ 254.0633 found254.0625.

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Methyl (E)-[3-(Pentafluorosulfanyl)allyl]-L-prolinate (4b): Follow-ing the general Tsuji–Trost procedure, 4b was isolated as a paleyellow oil (11 mg, 27 %) after purification by flash chromatographyusing hexane/Et2O (90:10) as the eluent. Following the general nu-cleophilic substitution procedure, 4b was isolated as pale yellowoil (26 mg, 59 %) after purification by flash chromatography usinghexane/Et2O (70:30) as the eluent. IR (ATR, ZnSe): ν̃ = 2953, 2849,1734, 1437, 1198, 1172, 827, 724 cm–1. 1H NMR (500 MHz, CDCl3):δ = 6.64–6.52 (m, 2 H), 3.71 (s, 2 H), 3.48–3.42 (m, 1 H), 3.30–3.20(m, 2 H), 3.18–3.12 (m, 1 H), 2.47–2.41 (m, 1 H), 2.20–2.10 (m, 1 H),2.01–1.90 (m, 2 H), 1.89–1.79 (m, 1 H) ppm. 13C NMR (126 MHz,CDCl3): δ = 174.3, 142.1 (p, J = 20.2 Hz), 136.1 (p, J = 6.3 Hz), 65.4,53.90, 53.86, 52.1, 29.7, 23.5 ppm. 19F NMR (470 MHz, CDCl3): δ =84.0–82.7 (m, 1 F), 62.9 (dd, J = 150, 5.3 Hz, 4 F) ppm. HRMS ESI+

calcd. for C9H15F5NO2S [M + H]+ 296.0738 found 296.0724.(E)-N,N-Bis{2-[(tert-butyldimethylsilyl)oxy]ethyl}-3-(penta-fluorosulfanyl)prop-2-en-1-amine (4c): Following the generalTsuji–Trost procedure, 4c was isolated as a pale yellow oil (32 mg,54 %) after purification by flash chromatography using hexane/Et2O(98:2) as the eluent. Following the general nucleophilic substitutionprocedure, 4c was isolated as a pale yellow oil (61 mg, 83 %) afterpurification by flash chromatography using hexane/Et2O (90:10) asthe eluent. IR (ATR, ZnSe): ν̃ = 2354, 2929, 2857, 1472, 1252, 1098,825, 660 cm–1. 1H NMR (500 MHz, CDCl3): δ = 6.69 (dpt, J = 14.5,6.6, 1.6 Hz, 1 H), 6.50 (dtp, J = 14.5, 5.3,1.1 Hz, 1 H), 3.68 (t, J =6.0 Hz, 4 H), 3.44–3.40 (m, 2 H), 2.68 (t, J = 6.0 Hz, 4 H), 0.89 (s, 18H), 0.05 (s, 12 H) ppm. 13C NMR (126 MHz, CDCl3): δ = 141.9 (p, J =19.3 Hz), 137.3 (p, J = 6.3 Hz), 62.2, 57.0, 55.3, 26.0, 18.4, –5.3 ppm.19F NMR (470 MHz, CDCl3): δ = 84.9–83.6 (m, 1 F), 63.3 (dd, J = 150,6.5 Hz, 4 F) ppm. HRMS ESI+ calcd. for C19H43F5NO2SSi2 [M + H]+

500.2468 found 500.2452.N-Cinnamyl-N-[(E)-3-(pentafluorosulfanyl)allyl]butan-1-amine(4d): Following the general Tsuji–Trost procedure, 4d was isolatedas a colourless oil (28 mg, 67 %) after purification by flash chroma-tography using hexane/Et2O (98:2) as the eluent. Following the gen-eral nucleophilic substitution procedure, 4d was isolated as a paleyellow oil (40 mg, 75 %) after purification by flash chromatographyusing hexane/Et2O (93:7) as the eluent. IR (ATR, ZnSe): ν̃ = 2928,2863, 2801, 1449, 1362, 887, 719, 691 cm–1. 1H NMR (500 MHz,CDCl3): δ = 7.39–7.36 (m, 1 H), 7.35–7.30 (m, 2 H), 7.26–7.22 (m, 1H), 6.67–6.58 (m, 1 H), 6.57–6.49 (m, 2 H), 6.22 (dt, J = 15.9, 6.7 Hz,1 H), 3.27–3.24 (m, 4 H), 2.52–2.48 (m, 2 H), 1.51–1.44 (m, 2 H), 1.38–1.30 (m, 2 H), 0.93 (t, J = 7.3 Hz, 3 H) ppm. 13C NMR (126 MHz,CDCl3): δ = 142.0 (p, J = 19.6 Hz), 137.0, 136.9 (p, J = 6.5 Hz), 133.1,128.7, 127.7, 126.8, 126.4, 56.7, 53.9, 53.2, 29.8, 20.6, 14.1 ppm. 19FNMR (470 MHz, CDCl3): δ = 84.5–83.3 (m, 1 F), 63.1 (dd, J = 150,5.7 Hz, 4 F) ppm. HRMS ESI+ calcd. for C16H23F5NS [M + H]+ 356.1466found 356.1448.(E)-N-Benzyl-N-methyl-3-(pentafluorosulfanyl)prop-2-en-1-amine (4e): Following the general Tsuji–Trost procedure, 4e wasisolated as a colourless oil (19 mg, 56 %) after purification by flashchromatography using pentane/Et2O (90:10) as the eluent. Follow-ing the general nucleophilic substitution procedure, 4e was isolatedas a pale yellow oil (36 mg, 85 %) after purification by flash chroma-tography using hexane/Et2O (90:10) as the eluent. IR (ATR, ZnSe):ν̃ = 3029, 2793, 1453, 1365, 1027, 891, 827, 696 cm–1. 1H NMR(500 MHz, CDCl3): δ = 7.38–7.27 (m, 2 H), 6.64 (dpt, J = 14.5, 6.4,1.6 Hz, 1 H), 6.54 (dtp, J = 14.5, 5.7, 1 Hz, 1 H), 3.55 (s, 2 H), 3.15(dh, J = 5.7, 2.0 Hz, 2 H), 2.26 (s, 3 H) ppm. 13C NMR (126 MHz,CDCl3): δ = 142.1 (p, J = 19.7 Hz), 138.3, 136.6 (p, J = 6.9 Hz), 129.0,128.6, 127.5, 62.1, 56.3, 42.5 ppm. 19F NMR (470 MHz, CDCl3): δ =85.1–82.2 (m, 1 F), 63.0 (dd, J = 150, 6.5 Hz, 4 F) ppm. HRMS ESI+

calcd. for C11H15F5NS [M + H]+ 288.0834 found 288.0835.

Eur. J. Org. Chem. 2016, 4611–4620 www.eurjoc.org © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim4618

(E)-N,N-Dibenzyl-3-(pentafluorosulfanyl)prop-2-en-1-amine(4f): Following the general Tsuji–Trost procedure, 4f was isolatedas a pale yellow oil (32 mg, 76 %) after purification by flash chroma-tography using hexane/CH2Cl2/Et2O (80:15:5) as the eluent. Follow-ing the general nucleophilic substitution procedure, 4f was isolatedas colourless oil (45 mg, 85 %) after purification by flash chromatog-raphy using hexane/Et2O (90:10) as the eluent. IR (ATR, ZnSe): ν̃ =3061, 3027, 2802, 1494, 1366, 1028, 731, 695 cm–1. 1H NMR(500 MHz, CDCl3): δ = 7.38–7.33 (m, 8 H), 7.30–7.26 (m, 2 H), 6.63–6.49 (m, 2 H), 3.63 (s, 4 H), 3.20 (m, 2 H) ppm. 13C NMR (126 MHz,CDCl3): δ = 142.0 (p, J = 19.9 Hz), 138.6, 136.6 (p, J = 6.8 Hz), 128.8,128.6, 127.5, 58.5, 52.7 ppm. 19F NMR (470 MHz, CDCl3): δ = 84.4–83.1 (m, 1 F), 63.0 (dd, J = 150, 6.1 Hz, 4 F) ppm. HRMS ESI+ calcd.for C17H19F5NS [M + H]+ 364.1153 found 364.1145.

(E)-2-{Benzyl[3-(pentafluorosulfanyl)allyl]amino}ethan-1-ol(4g): Following the general Tsuji–Trost procedure, 4g was isolatedas a colourless oil (16 mg, 44 %) after purification by flash chroma-tography using hexane/CH2Cl2/Et2O (50:30:20) as the eluent. Follow-ing the general nucleophilic substitution procedure, 4g was isolatedas a pale yellow oil (30 mg, 63 %) after purification by flash chroma-tography using hexane/Et2O (50:50) as the eluent. IR (ATR, ZnSe):ν̃ = 3395, 3030, 2922, 1452, 1027, 886, 912, 718 cm–1. 1H NMR(500 MHz, CDCl3): δ = 7.39–7.27 (m, 5 H), 6.60–3.47 (m, 2 H), 3.67–3.63 (m, 3 H), 3.29–3.26 (m,2 H), 2.75–2.69 (m, 2 H), 2.34 (br. s, 1 H)ppm. 13C NMR (126 MHz, CDCl3): δ = 142.5 (p, J = 20.0 Hz), 137.9,135.7 (p, J = 6.8 Hz), 129.0, 128.8, 127.7, 59.0, 58.4, 55.5, 53.1 ppm.19F NMR (470 MHz, CDCl3): δ = 83.9–82.6 (m, 1 F), 62.9 (dd, J = 150,5.6 Hz) ppm. HRMS ESI+ calcd. for C12H17F5NOS [M + H]+ 318.0946found 318.0939.

(E)-N-Benzyl-3-(pentafluorosulfanyl)prop-2-en-1-amine (4h):Following the general nucleophilic substitution procedure, 4h wasisolated as a yellow oil (35 mg, 86 %) after purification by flashchromatography using hexane/Et2O (80:20) as the eluent. IR (ATR,ZnSe): ν̃ = 3030, 2837, 1454, 1126, 885, 819, 723, 695 cm–1. 1H NMR(500 MHz, CDCl3): δ = 7.38–7.27 (m, 5 H), 6.65 (dpt, J = 14.5, 6.4,1.7 Hz, 1 H), 6.56 (dtp, J = 14.5, 5.1, 1 Hz, 1 H), 3.81 (s, 2 H), 3.43–3.40, (m, 2 H), 1.46 (br. s, 1NH) ppm. 13C NMR (126 MHz, CDCl3): δ =141.4 (p, J = 20.3 Hz), 139.5, 137.4 (p, J = 6.9 Hz), 128.7, 128.2, 127.5,53.4, 48.0 ppm. 19F NMR (470 MHz, CDCl3): δ = 84.87–82.93 (m, 1F), 63.2 (dd, J = 150, 5.8 Hz, 4 F) ppm. HRMS ESI+ calcd. forC10H13F5NS [M + H]+ 274.0683 found 274.0665.

(E)-N-(4-Methoxybenzyl)-3-(pentafluorosulfanyl)prop-2-en-1-amine (4i): Following the general nucleophilic substitution proce-dure, 4i was isolated as a yellow oil (37 mg, 83 %) after purificationby flash chromatography using CH2Cl2/Et2O (80:20) as the eluent.IR (ATR, ZnSe): ν̃ = 2914, 2836, 1611, 1511, 1244, 1033, 826,654 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.25–7.21 (m, 2 H), 6.90–6.86 (m, 2 H), 6.69–6.60 (m, 1 H), 6.60–6.51 (m, 1 H), 3.81 (s, 3 H),3.74 (s, 2 H), 3.41–3.38 (m, 2 H) ppm. 13C NMR (126 MHz, CDCl3):δ = 159.0, 141.4 (p, J = 20.1 Hz), 137.4 (p, J = 6.8 Hz), 131.6, 129.5,114.1, 55.4, 52.8, 47.9 ppm. 19F NMR (470 MHz, CDCl3): δ = 84.7–83.1 (m, 1 H), 63.2 (dd, J = 150, 5.7 Hz) ppm. HRMS ESI+ calcd. forC12H17F5NOS [M + H]+ 318.0946 found 318.0939.

(E)-N-[3-(Pentafluorosulfanyl)allyl]-4-phenylbutan-1-amine (4j):Following the general nucleophilic substitution procedure, 4j wasisolated as a yellow oil (36 mg, 77 %) after purification by flashchromatography using CH2Cl2/CH3OH (99.5:0.5) as the eluent. IR(ATR, ZnSe): ν̃ = 3028, 2937, 2858, 1454, 1134, 884, 821, 696 cm–1.1H NMR (500 MHz, CDCl3): δ = 7.31–7.25 (m, 2 H), 7.21–7.16 (m, 3H), 6.65–6.49 (m, 2 H), 3.40–3.36 (m, 2 H), 2.66–2.60 (m, 4 H), 1.71–1.63 (m, 2 H), 1.57–1.49 (m, 2 H), 1.17 (br. s, 1NH) ppm. 13C NMR

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(126 MHz, CDCl3): δ = 142.4, 141.2 (p, J = 20.0 Hz), 137.6 (p, J =6.5 Hz), 128.5, 128.5, 125.9, 49.5, 48.9, 35.9, 29.8, 29.1 ppm. 19F NMR(470 MHz, CDCl3): δ = 84.6–83.3 (m), 63.2 (dd, J = 150, 5.4 Hz) ppm.HRMS ESI+ calcd. C13H19F5NS [M + H]+ 316.1153 found 316.1155.

(E)-4-Butyl-N-[3-(pentafluorosulfanyl)allyl]aniline (4k): Followingthe general nucleophilic substitution procedure, 4k was isolated asa yellow oil (36 mg, 76 %) after purification by flash chromatogra-phy using hexane/Et2O (90:10) as the eluent. IR (ATR, ZnSe): ν̃ =3410, 2928, 2858, 1615, 1518, 892, 826, 766 cm–1. 1H NMR (500 MHz,CDCl3): δ = 7.07–7.00 (m, 2 H), 6.73–6.57 (m, 2 H), 6.58–6.51 (m, 2H), 3.97–3.93 (m, 2 H), 3.76 (br. s, 1NH), 2.56–2.47 (m, 2 H), 1.56 (tt,J = 9.1, 6.9 Hz, 2 H), 1.35 (h, J = 7.4 Hz, 2 H), 0.93 (t, J = 7.4 Hz, 3H) ppm. 13C NMR (126 MHz, CDCl3): δ = 144.8, 141.7 (p, J = 20.3 Hz),136.6 (p, J = 6.7 Hz), 133.3, 129.5, 113.1, 44.2, 34.8, 34.1, 22.5, 14.1ppm. 19F NMR (470 MHz, CDCl3): δ = 84.6–82.8 (m, 1 F), 63.6 (dd,J = 150, 5.0 Hz, 4 F) ppm. HRMS ESI+ calcd. for C13H19F5NS [M + H]+

316.1153 found 316.1160.

(E)-N-(Furan-2-ylmethyl)-3-(pentafluorosulfanyl)prop-2-en-1-amine (4l): Following the general nucleophilic substitution proce-dure, 4l was isolated as a yellow oil (26 mg, 67 %) after purificationby flash chromatography using CH2Cl2/Et2O (80:20) as the eluent.IR (ATR, ZnSe): ν̃ = 2924, 2852, 1460, 1148, 882, 819, 724,654 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.37 (dd, J = 1.8, 0.8 Hz, 1H), 6.63 (dpt, J = 14.5, 6.3, 1.7 Hz, 1 H), 6.52 (dtp, J = 14.5, 5.3, 1 Hz),6.32 (dd, J = 3.2, 1.9 Hz, 1 H), 6.20–6.18 (m, 1 H), 3.79 (s, 2 H), 3.40(dh, J = 4.1, 2.3 Hz, 2 H) ppm. 13C NMR (126 MHz, CDCl3): δ = 153.1,142.3, 141.5 (p, J = 19.8, 19.3 Hz), 137.1 (p, J = 6.9 Hz), 110.4, 107.6,47.7, 45.6 ppm. 19F NMR (470 MHz, CDCl3): δ = 84.6–82.8 (m, 1 F),63.1 (dd, J = 151, 6.2 Hz, 4 F) ppm. HRMS ESI+ calcd. for C8H11F5NOS[M + H]+ 264.0476 found 264.0463.

(E)-N-Methyl-N-[3-(pentafluorosulfanyl)allyl]aniline (4m): Fol-lowing the general Tsuji–Trost procedure, 4m was isolated as a col-ourless oil (22 mg, 69 %) after purification by flash chromatographyusing hexane/CH2Cl2/Et2O (90:8:2) as the eluent. Following the gen-eral nucleophilic substitution procedure, 4m was isolated as a yel-low oil (28 mg, 69 %) after purification by flash chromatographyusing hexane/Et2O (90:10) as the eluent. IR (ATR, ZnSe): ν̃ = 3066,2885, 1599, 1504, 1349, 888, 748, 669 cm–1. 1H NMR (500 MHz,CDCl3): δ = 7.29–7.25 (m, 2 H), 6.94 (m, 1 H), 6.71 (m, 2 H), 6.57–6.48 (m, 2 H), 4.07 (m, 2 H), 2.96 (s, 3 H) ppm. 13C NMR (126 MHz,CDCl3): δ = 148.8, 141.7 (p, J = 20.3 Hz), 135.1 (p, J = 6.6 Hz), 129.5,117.9, 112.7, 53.0, 38.5 ppm. 19F NMR (470 MHz, CDCl3): δ = 84.2–82.9 (m, 1 F), 63.6 (d, J = 151.8 Hz, 4 F) ppm. HRMS ESI+ calcd. forC10H13F5NS [M + H]+ 274.0683 found 274.0677.

(E)-N-Allyl-N-[3-(pentafluorosulfanyl)allyl]aniline (4n): Followingthe general Tsuji–Trost procedure, 4n was isolated as a yellow oil(27 mg, 76 %) after purification by flash chromatography using hex-ane/Et2O (95:5) as the eluent. Following the general nucleophilicsubstitution procedure, 4n was isolated as a yellow oil (8.6 mg,19 %) after purification by flash chromatography using hexane/Et2O(99:1) as the eluent. IR (ATR, ZnSe): ν̃ = 3063, 2923, 1598, 1504,1233, 825, 744, 689 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.28–7.23(m, 2 H), 7.68 (tt, J = 7.6, 1.0 Hz, 1 H), 6.72–6.68 (m, 2 H), 6.58–6.49(m, 2 H), 5.86 (ddt, J = 17.0, 10.1, 5.0 Hz, 1 H), 5.24–5.17 (m, 2 H),4.08 (m, 2 H), 3.94 (dt, J = 5.1, 1.7 Hz) ppm. 13C NMR (126 MHz,CDCl3): δ = 147.9, 141.7 (p, J = 19.9 Hz), 135.2 (p, J = 6.6 Hz), 133.2,129.5, 117.8, 117.1, 112.7, 53.0, 50.3 ppm. 19F NMR (470 MHz, CDCl3):δ = 84.2–83.0 (m, 1 F) 63.7 (d, J = 153.2 Hz, 4 F) ppm. HRMS ESI+

calcd. for C12H15F5NS [M + H]+ 300.0840 found 300.0825.

(E)-N-Benzyl-N-[3-(pentafluorosulfanyl)allyl]-4-phenoxyaniline(4o): Following the general Tsuji–Trost procedure, 4o was isolated

Eur. J. Org. Chem. 2016, 4611–4620 www.eurjoc.org © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim4619

as a pale yellow oil (38 mg, 73 %) after purification by flash chroma-tography using hexane/Et2O (98:2) as the eluent. Following the gen-eral nucleophilic substitution procedure, 4o was isolated as paleyellow oil (18 mg, 28 %) after purification by flash chromatographyusing hexane/Et2O (90:10) as the eluent. IR (ATR, ZnSe): ν̃ = 3039,2916, 1588, 1508, 1487, 1225, 827, 690 cm–1. 1H NMR (500 MHz,CDCl3): δ = 7.37–7.33 (m, 2 H), 7.32–7.26 (m, 3 H), 7.26–7.23 (m, 2H), 7.03 (tt, J = 7.6, 1.1 Hz, 1 H), 6.98–6.92 (m, 4 H), 6.73–6.69 (m, 2H), 6.55–6.50 (m, 2 H), 4.52 (s, 2 H), 4.12–4.11 (m, 2 H) ppm. 13CNMR (126 MHz, CDCl3): δ = 158.7, 148.6, 144.8, 142.0 (p, J = 20.3 Hz),137.8, 134.8 (p, J = 6.6 Hz), 129.7, 128.9, 127.5, 127.0, 122.4, 121.1,117.6, 114.3, 54.8, 50.8 ppm. 19F NMR (470 MHz, CDCl3): δ = 84.1–82.8 (m, 1 F), 63.6 (d, J = 151.3 Hz, 4 F) ppm. HRMS ESI+ calcd. forC22H21F5NOS [M + H]+ 442.1259 found 442.1244.

(E)-[3-(Dodecylthio)prop-1-en-1-yl]pentafluorosulfane (5a): Fol-lowing the general nucleophilic substitution procedure but usingacetonitrile as solvent and heating at 60 °C, 5a was isolated ascolourless oil (42 mg, 79 %) after purification by flash chromatogra-phy using pentane as the eluent. IR (ATR, ZnSe): ν̃ = 2922, 2853,1465, 957, 919, 834 cm–1. 1H NMR (500 MHz, CDCl3): δ = 6.54–6.44(m, 2 H), 3.19 (dh, J = 3.5, 1.7 Hz, 2 H), 2.46 (t, J = 7.4 Hz, 2 H), 1.59–1.52 (m, 2 H), 1.40–1.32 (m, 2 H), 1.30–1.22 (m, 16 H), 0.88 (t, J =6.9 Hz, 3 H) ppm. 13C NMR (126 MHz, CDCl3): δ = 141.6 (p, J =20.1 Hz), 135.2 (p, J = 7.1 Hz), 32.1, 31.5, 31.4, 29.79, 29.78, 29.7,29.6, 29.5, 29.32, 29.31, 28.9, 22.8, 14.3 ppm. 19F NMR (470 MHz,CDCl3): δ = 83.2 (m, 1 F), 63.4 (d, J = 150.1 Hz, 4 F) ppm. HRMS ESI+

calcd. for C15H29F5S2 [M + H]+ 369.1704 found 369.1693.

(E)-Pentafluoro[3-(phenylthio)prop-1-en-1-yl]sulfane (5b): Fol-lowing the general nucleophilic substitution procedure but usingacetonitrile as solvent and heating at 60 °C, 5b was isolated as acolourless oil (76 % NMR, 10 mg, 24 %) after purification by flashchromatography using pentane as the eluent. IR (ATR, ZnSe): ν̃ =2926, 1713, 1439, 1220, 814, 819, 738, 689 cm–1. 1H NMR (500 MHz,CDCl3): δ = 7.40–7.37 (m, 2 H), 7.35–7.27 (m, 3 H), 6.50 (dtp, J =14.6, 7.4, 1.4 Hz, 1 H), 6.24 (dpt, J = 14.3, 6.5, 1.4 Hz, 1 H), 3.50 (dh,J = 7.5, 1.6 Hz, 2 H) ppm. 13C NMR (126 MHz, CDCl3): δ = 142.1 (p,J = 20.2 Hz), 134.0 (p, J = 7.0 Hz), 133.2, 132.6, 129.4, 128.1, 35.2ppm. 19F NMR (470 MHz, CDCl3): δ = 83.0 (m, 1 F), 63.2 (dd, J =150.7, 6.5 Hz, 4 F) ppm. HRMS APPI calcd. for C9H9F5S2 [M*]+

276.0060 found 276.0059.

Dibenzyl (E)-2-Methyl-2-[3-(pentafluorosulfanyl)allyl]malonate(6b): Following the general Tsuji–Trost procedure but using only1 equiv. of malonate, 6b was isolated as a colourless oil (27 mg,49 %) after purification by flash chromatography using hexane/Et2O(95:5) as the eluent. IR (ATR, ZnSe): ν̃ = 3035, 1728, 1455, 1229,1103, 830, 722, 694 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.35–7.31(m, 6 H), 7.27–7.23 (m, 4 H), 6.47–6.35 (m, 2 H), 5.12 (s, 4 H), 2.71–2.67 (m, 2 H), 1.47 (s, 3 H) ppm. 13C NMR (126 MHz, CDCl3): δ =170.7 (s), 143.4 (p, J = 19.8 Hz), 135.2, 133.8 (p, J = 7.1 Hz), 128.8,128.6, 128.3, 67.6, 53.5, 36.9, 20.4 ppm. 19F NMR (376 MHz, CDCl3):δ = 83.1 (m, 1 F), 62.5 (dd, J = 153.5, 6.8 Hz, 4 F) ppm. HRMS ESI+

calcd. for C21H21F5O4S [M + H]+ 465.1154 found 465.1149.

Dibenzyl (E)-2-Benzyl-2-[3-(pentafluorosulfanyl)allyl]malonate(6c): Following the general Tsuji–Trost procedure but using only1 equiv. of malonate, 6c was isolated as a colourless oil (39 mg,42 %) after purification by flash chromatography using hexane/Et2O(95:5) as the eluent. IR (ATR, ZnSe): ν̃ = 3033, 2957, 1727, 1455,1167, 833, 695 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.37–7.30 (m,6 H), 7.26–7.16 (m, 7 H), 6.97–6.93 (m, 2 H), 6.47–6.28 (m, 2 H), 5.17(d, J = 12.1 Hz, 2 H), 5.07 (d, J = 12.1 Hz, 2 H), 3.29 (s, 2 H), 2.59–2.54 (m, 2 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 169.8, 145.0–

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141.9 (m), 134.9, 134.3–132.9 (m), 130.0, 128.79, 128.76, 128.71,128.69, 127.5, 67.8, 39.5, 34.1 ppm. 19F NMR (470 MHz, CDCl3): δ =83.9–82.5 (m, 1 F), 62.6 (dd, J = 151.3, 6.1 Hz, 4 F) ppm. HRMS ESI+

calcd. for C27H25F5O4S [M + H]+ 541.1467 found 541.1458.

Dibenzyl 2,2-bis[(E)-3-(Pentafluorosulfanyl)allyl]malonate (8):Following the general Tsuji–Trost procedure, 8 was isolated as acolourless oil (26 mg, 71 %) after purification by flash chromatogra-phy using hexane/CH2Cl2/Et2O (90:8:2) as the eluent. IR (ATR, ZnSe):ν̃ = 3071, 2954, 1729, 1456, 1187, 824, 720 cm–1. 1H NMR (500 MHz,CDCl3): δ = 7.37–7.31 (m, 6 H), 7.25–7.21 (m, 4 H), 6.44–6.25 (m, 4H), 5.13 (s, 4 H), 2.69 (d, J = 7.1 Hz, 4 H) ppm. 13C NMR (126 MHz,CDCl3): δ = 168.9, 144.1 (p, J = 20.6 Hz), 134.6, 132.6 (p, J = 7.0 Hz),129.0, 128.9, 128.6, 68.2, 34. 9 ppm. 19F NMR (470 MHz, CDCl3): δ =83.2–81.7 (m, 1 F), 62.4 (dd, J = 150.4, 5.9 Hz, 4 F) ppm. HRMS ESI+

calcd. for C23H22F10O4S2 [M + NH4]+ 634.1144 found 634.1152.

AcknowledgmentsThis work was supported by the Natural Sciences and Engineer-ing Research Council of Canada (NSERC), the Fonds de recher-che du Québec - Nature et technologies (FRQNT) and the Uni-versité Laval.

Keywords: Synthetic methods · Nucleophilic substitution ·Fluorine · Organofluorine chemistry · Pentafluorosulfanyl ·Allylic compounds

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Received: June 3, 2016Published Online: August 23, 2016