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Electronic Supplementary Materials
Ugi Amine-Derived P, N- and P, P- Ligands with N-Alkyltriethoxysilyl Tethers: Synthesis and Evaluation of Mesoporous Silica-Supported Pd Complexes in Asymmetric Allylic Substitution Reactions
Roman G. Kultyshev and Akira Miyazawa* National Institute of Advanced Industrial Science and Technology (AIST),
Central 5, Higashi, Tsukuba, Ibaraki 305-8565, Japan Fax: +81-29-861-4566
E-mail: [email protected]
Contents 1. Experimental detailes of the synthetic approaches other than N-alkylation processes . pp 2- 8. 2. NMR spectra (1H, 13C, 31P and 31P MAS) of new compounds. PP 9 – 32.
1
Experimental details for the syntheses of N-Methyl aminoethanol O-allyl ether S1, and N-Methyl aminoethanol O-propyltriethoxysilyl ether S2.
OH
HN O
HN
Me O Si(OEt)3
HNa, b, c d, e
Me Me
a) Boc2O, THF, rt; b) NaH, allyl chloride, THF, 0 oC; c) H2SO4, CH2Cl2, 0 oC; d) (TMS)2NH, saccharin (cat), 130 oC; e) HSi(OEt)3, Karstedt cat., THF, 35 oC
S1 S2
N-Methyl aminoethanol O-allyl ether S1 A 100 mL round-bottomed flask (rbf) equipped with a magnetic stirbar was charged with THF (15 mL), water (15 mL) and 2-(methylamino)ethanol (2.00 mL, 25.0 mmol). To the stirred solution exposed to air Boc2O (5.9 g, 27 mmol) was added in 4 portions within 10 min resulting in gas evolution. Several drops of sat. aq. NaHCO3 were added 40 min later to keep the pH around 8. Most of THF was removed on a rotary evaporator 4.5 h after the Boc2O addition. The residue was transferred into a separatory funnel using EtOAc, washed with aq. 2.5 M NH4Cl (20 mL) and brine. The organic phase was dried over MgSO4, filtered into a 500 mL rbf and stripped of volatiles on the rotary evaporator. Using hexane transferred the crude product into a pre-weighed 100 mL rbf, removed volatiles on the rotary evaporator (20 mm Hg). N-Methyl-N-Boc-aminoethanol was obtained as colorless oil: 4.26 g (97%). A 3-neck rbf equipped with a magnetic stirbar, a rubber septum, a glass stopcock (Teflon tape, central neck) and connected to a vacuum line was charged with 4.26 g of the protected amine (24.3 mmol). After evacuation and refill with nitrogen 90 mL of THF freshly distilled from sodium-benzophenone ketyl was added. The flask was placed in an ice-water bath. Approx. 25 min later quickly added 1.09 g of 60% NaH (27.2 mmol) in paraffin via the central neck. Approx. 20 min later added allyl bromide (2.15 mL, 24.8 mmol) with a syringe via the rubber septum followed by 0.4487 g of tetrabutylammonium iodide (1.21 mmol, 5 mol%) via the central neck. Approx. 2.5 h later removed the cold bath and let the reaction mixture stirring for 16 h under nitrogen. The flask was immersed in ice-water bath followed by careful addition of water (20 mL, audible sound). The mixture was transferred into a 250 mL separatory funnel followed by addition of EtOAc (50 mL) and extraction. The organic phase was set aside and the aqueous phase was extracted with fresh portion of EtOAc (40 mL). The organic phases were combined, washed with aq. 2.5 M NH4Cl (50 mL) and brine, dried over MgSO4, filtered into a 500 mL rbf and stripped of volatiles on the rotary evaporator leaving behind yellow oil, which was chromatographed on silica (normal phase, EtOAc-hexane, 1:3) furnishing 3.7916 g of N-Methyl-N-Boc-aminoethanol O-allyl ether as colorless oil (72% yield). N-Boc deprotection was achieved according to the method of Strazzolini et al.1 To a 200 mL rbf charged with a magnetic stirbar and CH2Cl2 (22 mL) and immersed in an ice-water bath added 1.48 mL of conc. H2SO4 (assumed to be 17.9 M, 26.5 mmol) with stirring. The central neck was plugged with a glass stopcock while a dropping funnel was attached to the side-neck. A solution of 3.79 g of N-Methyl-N-Boc-aminoethanol O-allyl ether (17.6 mmol) in 65 mL CH2Cl2 was added to the solution of acid dropwise from the addition funnel within 45 min followed by removal of cold bath and stirring at rt for 6 h. The dark purple mixture was transferred into a separatory funnel
2
and extracted with water (40 mL). The organic phase was extracted with additional 40 mL of water, after which the aqueous extracts were combined in a 200 mL Erlenmeyer flask and basified by addition of NaOH (3.245 g in 15 mL water) with stirring. The resulting solution was saturated with NaCl and extracted with three 50 mL portions of CH2Cl2. Combined extracts were dried over Na2SO4, filtered into a 500 mL rbf and stripped of the solvent on the rotary evaporator (200 mm Hg). The resulting yellowish oil was fractionated in vacuo using a one-piece distillation head and a receiving flask held at -50 oC. The title compound was obtained as colorless oil (1.2208 g, 60% yield). 1H NMR (CDCl3): 5.91 (ddt, J = 17.4; 10.4; 5.7, 1H, CH=CH2), 5.29-5.15 (m, 2H, CH=CH2), 3.98 (dt, J = 5.8; 1.4, 2H, OCH2CH=CH2), 3.56-3.52 (m, 2H, NCH2CH2O), 2.77-2.73 (m, 2H, NCH2CH2), 2.44 (s, 3H, NCH3), 1.65 (br s, 1H, NH). Synthesis of N-methyl aminoethanol O-propyltriethoxysilyl ether S2, First, S1 was converted to its N-TMS derivative via the procedure by Bruynes et al.2 A 50 mL 2-neck rbf equipped with a magnetic stirbar and a rubber septum was charged with 8.8 mg of saccharine (5.4 ml%) and 1.027 g (8.92 mmol) of S1. A condenser was attached to the central neck, the top of the condenser being connected to a vacuum line via a glass adapter. After cooling the flask (- 196 oC) it was evacuated and refilled with nitrogen. To the mixture added 1.45 mL of hexamethyldisilazane (6.95 mmol) freshly distilled from CaH2. After turning on the stirring and cooling the flask was placed into a 60 oC oil bath. Within 50 min the bath temperature was gradually increased to 130 oC. The flask was removed from the bath 3.5 h later and let cool down overnight under nitrogen. The silylated product was collected by pumping on the mixture through a trap kept at – 80 oC. Using liquid nitrogen bath condensed the product into a new apparatus comprised of a 50 mL 2-neck rbf equipped with a magnetic stirbar and a condenser. Upon completion of the transfer the side-neck was plugged with a rubber septum, the flask was cooled down (- 196 oC), evacuated and refilled with nitrogen. Dry toluene (10 mL) was added followed by 10 drops of a solution of Karstedt’s catalyst in xylene (2.1-2.4% wt. Pt, Gelest) and 1.30 mL of triethoxysilane. The flask was immersed into a 36 oC oil bath and kept at this temperature for 46 h. The mixture was pumped on through a - 196 oC trap for 2 h leaving behind colorless oil, which was kept under nitrogen overnight and weighed in air next morning (1.208 g). 1H NMR of the oil indicated complete hydrosilylation of the double bond and N-desilylation (61% yield). 1H NMR (CDCl3): 3.72 (q, J = 7.0, 6H, SiOCH2), 3.45-3.41 (m, 2H, CH2O), 3.31 (t, J = 6.9, 2H, CH2O), 2.65-2.62 (m, 2H, NCH2), 2.35 (s, 3H, NCH3), 1.72 (br s, 1H, NH), 1.63-1.55 (m, 2H, CH2CH2CH2), 1.13 (t, J = 7.0, 9H, OCH2CH3), 0.57-0.51 (m, 2H, CH2Si). Experimetal detales for the syntheses and attempted hydrosilylations of N-methyl-N-(1”-(3”-oxa-5”-hexenyl))-1-[1’, 2-bis(diphenylphosphino)ferrocenyl]ethylamine, S3; N-methyl-N-(1’-(3’-oxa-5’-hexenyl))-1-[2-(diphenylphosphinyl)ferrocenyl]- ethylamine, S4; and N-methyl-N-(1’-(5’-hexenoyl))-1-[2-(diphenylphos-phinyl)ferrocenyl]ethylamine, S7.
3
Fe PPh2
OAc
2a
3a
Fe PPh2
OAc
PPh2
S3
Fe PPh2
PPh2
ONMe b
Si(OEt)3
3e
Fe PPh2
PPh2
ONMe
Fe P(O)Ph2
OAc
S6
S4
Fe P(O)Ph2
ONMe
S5
Fe P(O)Ph2
ONMe
Si(OEt)3
a
c
e
a) S1 (excess), MeOH, reflux; b) HSi(OEt)3, Karstedt cat., toluene, 44 oC; c) H2O2, acetone-CH2Cl2 (1:3), rt; d) S1 (excess), i-PrOH-water (2.5:1), 85 oC; i) HSi(OEt)3, Karstedt cat., THF, 35 oC; j) MeNH2 (40% aq), i-PrOH, 50 oC; k) DCC/ Py/ THF; l) HSi(OEt)3, Karstedt cat., THF, 36 oC
S7
Fe P(O)Ph2
NMe
O
j, k
S8
Fe P(O)Ph2
NMe
Si(OEt)3
O
l
d
Synthesis and attempted hydrosilylation of N-methyl-N-(1”-(3”-oxa-5”-hexenyl))-1-[1’, 2-bis(diphenylphosphino)ferrocenyl]ethylamine, S3.3 A 50 mL 2-neck round-bottomed flask equipped with a magnetic stirbar, a reflux condenser and a rubber septum was charged with 0.2940 g of 3a (0.4590 mmol). Under nitrogen i-PrOH (5.0 mL) and water (2.0 mL) were added followed by S1 (6.15 mmol). The flask was immersed into an oil bath at 85 oC. After heating for 3 h and cooling to rt volatiles were removed by pumping through a -196 oC trap. The residue was chromatographed on silica (normal phase) using EtOAc-hexane (1:3). After trituration with hexane and pumping on the residual solid through a -196 oC trap (3-4 h) the product was obtained as orange crystals (0.2775 g, 87% yield). 1H NMR (CDCl3): 7.53-7.44 (m, 2H, C6H5), 7.35-7.05 (m, 18H, C6H5), 5.85-5.73 (m, 1H, CH=CH2), 5.21-5.07 (m, 1H, CH=CH2), 4.40-4.33 (m, 2H, Cp), 4.18 (br q, 1H, CHCH3), 4.10-4.04 (m, 2H, Cp), 3.96 (br s, 1H, Cp), 3.75-3.60 (m, 3H, OCH2CH=CH2 + Cp), 3.50 (br s, 1H, Cp), 3.00-2.90 (m, 1H, NCH2CHaO), 2.73-2.63 (m, 1H, NCH2CHbO), 2.58-2.48 (m, 1H, NCHaCH2), 2.40-2.30 (m, 1H, NCHbCH2), 1.74 (s, 3H, NCH3), 1.16 (d, J = 6.6, 3H, CHCH3). Under nitrogen to a stirred solution of S3 (0.1378 g, 0.1980 mmol) in dry toluene (0.5 mL) was added a drop of a solution of Karstedt’s catalyst in PDMSO (2.1-2.4% wt. Pt, Gelest) followed by 60.0 μL of triethoxysilane (0.33 mmol). The mixture was heated at 44 oC for 25 h. Removal of volatiles by pumping on the mixture through a - 196 oC trap resulted in a solid, its 1H NMR spectrum being identical to that of S3. Synthesis and attempted hydrosilylation of N-methyl-N-(1’-(3’-oxa-5’-hexenyl))-1-[2-(diphenylphosphinyl)ferrocenyl]ethylamine, S4. A 100 mL rbf equipped with a magnetic stirbar was charged with 0.4594 g of 2a (1.007 mmol). Upon addition of CH2Cl2 (3 mL) and acetone (9 mL) 2a dissolved. Hydrogen peroxide (30%, 0.41 mL) was added to the stirred solution within 3 min. After stirring for
4
30 min sat. aq. Na2S2O3 was added, and the mixture was extracted with CH2Cl2 (20 mL). The organic phase was washed with brine, dried over Na2SO4, filtered into a 200 mL rbf and stripped off volatiles on the rotary evaporator. Yellow foam formed was co-evaporated with hexane furnishing acetate-phosphine oxide S6 as a yellow solid (0.4002 g), which was used in the next step without further purification. 1H NMR (CDCl3): 7.79-7.72 (m, 2H, C6H5), 7.63-7.56 (m, 2H, C6H5), 7.55-7.35 (m, 6H, C6H5), 6.26 (q, J = 6.4, 1H, CHCH3), 4.64 (m, 1H, C5H3), 4.41 (q, J = 2.5, 1H, C5H3), 4.24 (s, 5H, C5H5), 3.96 (m, 1H, C5H3), 1.60 (d, J = 6.4, 3H, CHCH3), 1.20 (s, 3H, C(O)CH3). 31P{1H} NMR (CDCl3): 30.2. Amine-phosphine oxide S4 was obtained from 0.4749 g of S6 (1.005 mmol) and excess S1 (8.0 mmol) using the procedure described above for the preparation of S3. After chromatography of a crude product on silica (normal phase) using EtOAc-methanol (9:1) dark-red oil was obtained (0.4273 g, 80% yield). 1H NMR (CDCl3): 7.81-7.73 (m, 2H, C6H5), 7.60-7.29 (m, 8H, C6H5), 5.79 (ddt, J = 17.2; 10.4; 5.6, 1H, CH=CH2), 5.19-5.07 (m, 2H, CH=CH2), 4.49-4.42 (m, 2H, CHCH3 + C5H3), 4.29 (q, J = 2.4, 1H, C5H3), 4.16 (s, 5H, C5H5), 3.90 (m, 1H, C5H3), 3.70 (qdt, J = 12.5; 5.6; 1.5, 2H, OCH2CH=CH2), 2.90-2.82 (m, 1H, NCH2CHaO), 2.58-2.51 (m, 1H, NCH2CHbO), 2.48-2.40 (m, 1H, NCHaCH2), 2.35-2.27 (m, 1H, NCHbCH2), 1.74 (s, 3H, NCH3), 1.21 (d, J = 6.8, 3H, CHCH3). To a solution of S4 (0.427 g, 0.809 mmol) in dry toluene (3.0 mL) the Karstedt’s catalyst solution in xylene (2 drops) was added followed by 0.22 mL of triethoxysilane (1.2 mmol). After heating at 36 oC for 3 h the volatiles were removed by pumping through a -196 oC trap (1 h). 1H NMR of the residue indicated no conversion of S4 to S5 or any other product. Synthesis and hydrosilylation of N-methyl-N-(1’-(5’-hexenoyl))-1-[2-(diphenylphos-phinyl)ferrocenyl]ethylamine, S7. A 50 mL 2-neck round-bottomed flask equipped with a magnetic stirbar, a reflux condenser and a rubber septum was charged with 0.4966 g of S6 (1.051 mmol). Under nitrogen i-PrOH (10.0 mL) and methylamine (3.9 mL, 40% solution in water) were added into the flask followed by heating at 50 oC for 57 h,3 with addition of another 3.9 mL of methylamine solution in between (21 h after the commencement of heating). After pumping out volatiles through a -196 oC trap the residue was chromatographed on silica (normal phase) using EtOAc-MeOH-Et3N (9:1:0.5) as an eluent furnishing 0.3230 g of a desired amine-phosphine oxide (69% yield). Following the general procedure for the DCC-coupling between 2b and a carboxylic acid (vide supra) the amine-phosphine oxide (0.8005 g, 1.806 mmol) was reacted with 5-hexenoic acid (0.4154 g, 3.640 mmol) in THF (11 mL) in the presence of pyridine (3.59 mmol) and DCC (3.61 mmol). Crude amide-phosphine oxide S7 was purified by chromatography on silica (normal phase) with EtOAc as an eluent furnishing 0.7852 g of yellow solid (81% yield). 1H NMR (CDCl3, isomer ratio 3.3:1): 7.80-7.70 (m, 2H (major isomer), C6H5), 7.64-7.57 (m, 2H’ (minor isomer), C6H5), 7.56-7.32 (m, 8H + 8H’, C6H5), 5.84 (ddt, J = 17.2; 10.4; 6.6, 1H, CH=CH2), 5.75-5.59 (m; 1H’, CH=CH2 + 1H, CHCH3), 5.38 (br s, 1H’, CHCH3), 5.06-4.88 (m, 2H + 2H’, CH=CH2), 4.69 (br s, 1H’, C5H3), 4.58 (m, 1H, C5H3), 4.40 (q, J = 2.3, 1H, C5H3), 4.35 (m, 1H’, C5H3), 4.29 (s, 5H, C5H5), 4.21 (s, 5H’, C5H5), 3.94-3.88 (m, 1H + 1H’, C5H3), 3.00-2.90 (m, 1H, CHaCO), 2.32-2.22 (m, 1H, CHbCO), 2.13 (s, 3H, NCH3), 2.12 (s, 3H’, NCH3), 2.10-2.03 (m, 2H + 2H’, CH2), 1.93-1.80 (m, 2H’, CH2), 1.64-1.22 (m, 2H + 2H’, CH2CH2CH2), 1.51 (d, J = 6.8, 3H’, CHCH3), 1.46 (d, J = 6.8,
5
3H, CHCH3). To a solution of S7 (0.2643 g, 0.4900 mmol) in dry THF (3.0 mL) the Karstedt’s catalyst solution in xylene (2 drops) was added followed by 0.14 mL of triethoxysilane (0.77 mmol). After heating at 36 oC for 5 h volatiles were removed by pumping through a -196 oC trap (1 h). According to the 1H NMR spectrum of the residual oil the double bond of S7 was completely hydrosilylated, unlike those of S3 and S4 (vide supra), in agreement with the absence in the structure of S7 of any sites capable of binding the Pt center of Karstedt’s catalyst. Experimental detailes for the Syntheses of N-methyl-N-(n-hexyl)-1-[2-(diphenylphosphino)ferrocenyl]- ethylamine, 2g; N-methyl-N-(1’-(5’-hexenyl))-1-[2-(diphenylphosphino)- ferrocenyl]ethylamine, S11; and N-methyl-N-(1’-(5’-hexynyl)-1-[2- (diphenylphosphino)ferrocenyl]ethyl amine, S13; via acylation of 2b followed by LAH amide reduction.
Fe PPh2
NHMe
2b
DCC/ Py/ THF
S10, R = -CH=CH2
S12, R = -CCH
Fe PPh2
RNMe
O
RHO
O
Fe PPh2
RNMeLiAlH4
THF, reflux
S9, R = -CH2CH3
S11, R = -CH=CH2
S13, R = -CCH
2g, R = -CH2CH3
General procedure for the synthesis of P, N-ligands via DCC-coupling4 of 2b with a carboxylic acid followed by LAH reduction. Synthesis of N-methyl-N-(1’-(5’-hexenyl))-1-[2-(diphenylphosphino)ferrocenyl]ethylamine, S11. A 50 mL 2-neck round-bottomed flask equipped with a magnetic stirbar and a rubber septum was charged with 0.9161 g of 2b (2.144 mmol). THF (4.0 mL) was added under nitrogen, and the flask was placed in ice-water bath. 5-Hexenoic acid (0.4899 g, 4.292 mmol) in 4.0 mL of THF was added dropwise within 5 min followed by addition of pyridine (0.35 mL, 4.3 mmol) and a solution of DCC (0.8870 g, 4.299 mmol) in 4.0 mL THF. After cold bath removal the mixture was stirred overnight resulting in a precipitate, which was filtered off and washed with hexane to remove color. The filtrate and wash were combined and stripped off the volatiles. The residue was dissolved in dichloromethane, washed with 15% aq. KHSO4, brine and sat. aq. NaHCO3 (twice). The organic phase was dried over MgSO4 and filtered into a 200 mL flask containing 4.5 g of silica gel followed by removal of volatiles and co-evaporation with hexane. The resulting yellow powder was chromatographed on silica gel using EtOAc-hexane (1:2) as an eluent. Amide S10 was obtained in 88% yield (0.9906 g) as an orange hygroscopic solid. 1H NMR (CDCl3, approx. 4:1 mixture of isomers): 7.56-7.46 (m, 2H (major isomer) + 2H’ (minor isomer), C6H5), 7.39-7.30 (m, 3H + 3H’, C6H5), 7.25-7.15 (m, 5H + 3H’, C6H5), 7.08-7.02 (m, 2H’, C6H5), 6.11 (br quartet, J = 5.8, 1H, CHCH3), 5.87 (ddt, J = 17.0; 10.2; 6.7, 1H’, CH=CH2), 5.69 (ddt, J = 16.9; 10.2; 6.7, 1H, CH=CH2), 5.32 (qd, J = 6.8; 2.5, 1H’, CHCH3), 5.11-4.98 (m, 2H’, CH=CH2), 4.97-4.87 (m, 2H, CH=CH2), 4.51-4.46 (m, 1H + 1H’, C5H3), 4.35 (t, J = 2.4, 1H’, C5H3), 4.31 (t, J = 2.3, 1H, C5H3), 4.06 (s, 5H’, C5H5), 4.05 (s, 5H, C5H5), 3.83 (m, 1H’, C5H3), 3.79 (br s, 1H, C5H3), 2.80-2.70 (m, 1H’, CHaCO), 2.43-2.33 (m, 1H’, CHbCO), 2.20 (s, 3H’, NCH3), 2.17-2.06 (m; 3H, NCH3 + 2H’, CH2CH=CH2), 1.91-0.87 (m; 6H, (CH2)3 + 2H’, CH2CH2CH2), 1.53 (d, J = 6.8, 3H’, CHCH3), 1.42 (d, J = 6.8, 3H, CHCH3). Using THF (19 mL) the amide was transferred
6
into an apparatus comprised of a 50 mL 2-neck round-bottomed flask equipped with a magnetic stirbar, a reflux condenser and charged with LiAlH4 (0.353 g, 9.30 mmol). The resulting mixture was refluxed for 16 h under nitrogen followed by cooling in ice-water bath, careful addition of EtOAc (25 mL) and 6 mL 2.5 M aq. NH4Cl. The resulting mixture was filtered, and the color from the precipitate was washed out with EtOAc. The filtrate and wash were combined, dried over Na2SO4 and stripped off the volatiles after filtration. Crude amine S11 was purified by column chromatography (normal phase) using Et3N-EtOAc-hexane (1:10:10) as an eluent, co-evaporated with hexane and pumped on overnight to remove most of residual hexane (0.9379 g, 97% yield). 1H NMR (CDCl3): 7.61-7.54 (m, 2H, C6H5), 7.38-7.33 (m, 3H, C6H5), 7.19-7.09 (m, 5H, C6H5), 5.67 (ddt, J = 17.1; 10.2; 6.7, 1H, CH=CH2), 4.94-4.84 (m, 2H, CH=CH2), 4.39 (s, 1H, C5H3), 4.28-4.20 (m, 2H, CHCH3 + C5H3), 3.92 (s, 5H, C5H5), 3.85 (s, 1H, C5H3), 2.33-2.23 (m, 1H, NCHa), 2.18-2.09 (m, 1H, NCHb), 1.83 (q, J = 7.2, 2H, CH2CH=CH2), 1.69 (s, 3H, NCH3), 1.26 (d, 3H, CHCH3), 1.03 (quintet, J = 7.6, 2H, CH2CH2), 0.91-0.79 (m, 2H, CH2CH2). N-Methyl-N-(n-hexanoyl)-1-[2-(diphenylphosphino)ferrocenyl]ethylamine (S9). Prepared in 92% yield an orange hygroscopic solid according to the general procedure from 0.9157 g of 2b (2.1429 mmol). 1H NMR (CDCl3): 7.56-7.46 (m, 2H (major) + 2H’ (minor), C6H5), 7.40-7.30 (m, 3H + 3H’, C6H5), 7.25-7.15 (m, 5H + 3H’, C6H5), 7.08-7.02 (m, 2H’, C6H5), 6.11 (br quartet, 1H, CHCH3), 5.32 (qd, 1H’, CHCH3), 4.50-4.46 (m, 1H + 1H’, C5H3), 4.35 (t, J = 2.4, 1H’, C5H3), 4.31 (t, J = 2.4, 1H, C5H3), 4.07 (s, 5H’, C5H5), 4.05 (s, 5H, C5H5), 3.82 (m, 1H’, C5H3), 3.79 (m, 1H, C5H3), 2.76-2.66 (m, 1H’, CHaCO), 2.42-2.30 (m, 1H’, CHbCO), 2.20 (s, 3H’, NCH3), 2.14 (s, 3H, NCH3), 1.57-0.82 (m; 11H, CH3(CH2)4 + 9H’, CH3(CH2)3CH2). N-Methyl-N-(n-hexyl)-1-[2-(diphenylphosphino)ferrocenyl]ethylamine (2g). Prepared in 97% (crude yield) from S9 as dark-orange oil. In order to remove all hexane from 2g obtained after chromatography it was dissolved in 2 mL of CH2Cl2, passed through a short RF silica gel column (5.0 g) using acetonitrile as an eluent and stripped of volatiles by pumping on it through a –196 oC trap overnight. The 1H NMR of this product was identical to that of 2g prepared by the N-alkylation method (see main text). N-Methyl-N-(1’-(5’-Hexynoyl))-1-[2-(diphenylphosphino)ferrocenyl]ethylamine (S12). Hygroscopic orange solid, 86% yield. 1H NMR (CDCl3) : 7.56-7.46 (m, 2H (major) + 2H’ (minor), C6H5), 7.39-7.30 (m, 3H + 3H’, C6H5), 7.25-7.15 (m, 5H + 3H’, C6H5), 7.11-7.05 (m, 2H’, C6H5), 6.11 (br quartet, J = 5.6, 1H, CHCH3), 5.34 (quartet of d, J = 6.8; 2.4, 1H’, CHCH3), 4.51-4.46 (m, 1H + 1H’, C5H3), 4.35 (t, J = 2.4, 1H’, C5H3), 4.31 (t, J = 2.4, 1H, C5H3), 4.07 (s, 5H’, C5H5), 4.05 (s, 5H, C5H5), 3.83 (m, 1H’, C5H3), 3.78 (m, 1H, C5H3), 2.97-2.87 (m, 1H’, CHaCO), 2.55-2.46 (m, 1H’, CHbCO), 2.33-0.86 (m; 8H, (CH2)4 + 7H’, CH2(CH2)3CCH), 2.18 (s, 3H’, NCH3), 2.16 (s, 3H, NCH3), 1.88 (t, J = 2.6, 1H, CCH), 1.53 (d, J = 6.8, 3H’, CHCH3), 1.42 (d, J = 7.0, 3H, CHCH3). N-Methyl-N-(1’-(5’-hexynyl))-1-[2-(diphenylphosphino)ferrocenyl]ethylamine, (S13). Orange solid, 88% yield. 1H NMR (CDCl3): 7.61-7.54 (m, 2H, C6H5), 7.38-7.33 (m, 3H, C6H5), 7.19-7.09 (m, 5H, C6H5), 4.39 (s, 1H, C5H3), 4.28-4.20 (m, 2H, CHCH3 + C5H3), 3.92 (s, 5H, C5H5), 3.86 (s, 1H, C5H3), 2.36-2.27 (m, 1H, NCHa), 2.22-2.13 (m, 1H, NCHb), 2.00-1.84 (m, 3H, CH2 + CCH), 1.70 (s, 3H, NCH3), 1.27 (d, J = 6.8, 3H, CHCH3), 1.15-1.05 (m, 2H, CH2), 1.02-0.93 (m, 2H, CH2).
7
References
1. Strazzolini, P.; Misuri, N.; Polese, P. Tetrahedron Let. 2005, 46, 2075-2078. 2. Bruynes, C.; Jurriens, T. K. J. Org. Chem. 1982, 47, 3966-3969. 3. The procedure used here is analogous to the preparation of 2b from 2a and aq. methylamine,
see Boaz, N. W.; Debenham, S. D.; Mackenzie, E. B.; Large, S. E. Org. Lett. 2002, 4, 2421-2424.
4. The procedure was adopted from the DCC-coupling method reported in literature, see Belov, V. N.; Funke, C.; Labahn, T.; Es-Sayed, M.; de Meijere, A. Eur. J. Org. Chem. 1999, 1345-1356.
8
1H NMR of 2c
FePPh2
N
Si(OEt)3
13C NMR of 2c
FePPh2
N
Si(OEt)3
9
31P NMR of 2c
N
FePPh2
N
Si(OEt)3
1H NMR of 2d
PPh2HN
H Si(OEt)3
Fe
10
13C NMR of 2d
PPh2HN
H Si(OEt)3
Fe
31P NMR of 2d
PPh2HN
H Si(OEt)3
Fe
11
1H NMR of 2e
FePPh2
N
O
Si(OEt)3Si(OEt)3
13C NMR of 2e
FePPh2
N
O
Si(OEt)3Si(OEt)3
12
31P NMR of 2e
FePPh2
N
O
Si(OEt)3Si(OEt)3
1H NMR of 2g
PPh2HN
H
Fe
13
13C NMR of 2g
HN
Fe
PPh2HN
H
31P NMR of 2g
PPh HN
Fe
PPh2HN
H
14
1H NMR of 3c
N
FePPh2
N
Si(OEt)3
PPh2
13C NMR of 3c13C NMR of 3c
N
FePPh2
N
Si(OEt)3
PPh2
15
31P NMR of 3c
N
FePPh2
N
Si(OEt)3
PPh2
1H NMR of 3d
FePPh2
N
Si(OEt)PPh Si(OEt)3PPh2
16
13C NMR of 3d
FePPh2
N
Si(OEt)PPh Si(OEt)3PPh2
31P NMR of 3d
FePPh2
N
Si(OEt)PPh Si(OEt)3PPh2
17
1H NMR of 3e
FePPh2
N
O
Si(OEt)3PPh2 Si(OEt)3PPh2
13C NMR of 3e
FePPh2
N
O
Si(OEt)3PPh2 Si(OEt)3PPh2
18
31P NMR of 3e
FePPh2
N
O
Si(OEt)3PPh2 Si(OEt)3PPh2
1H NMR of the complex [(C3H5)Pd(2c)Cl] H
FePh2P
N
Pd+Cl-
Si(OEt)3
H
19
13C NMR of the complex [(C3H5)Pd(2c)Cl]H
FePh2P
N
Pd+Cl-
Si(OEt)3
31P NMR of the complex [(C3H5)Pd(2c)Cl]H
FePh2P
N
Pd+Cl-
Si(OEt)3
20
31P NMR of the complex [(C3H5)Pd(2c)Cl]H
FePh2P
N
Pd+Cl-
Si(OEt)3
1H NMR of the complex [(C3H5)Pd(2d)Cl]
Cl-
Ph2P NPd+
Cl
HSi(OEt)3
Fe
21
13C NMR of the complex [(C3H5)Pd(2d)Cl]
Pd+Cl-
Ph2P NPd+
HSi(OEt)3
Fe
31P NMR of the complex [(C3H5)Pd(2d)Cl]
Pd+Cl-
Ph2P NPd+
HSi(OEt)3
Fe
22
1H NMR of the complex [(C3H5)Pd(2e)Cl]H
FePh2P
NO
Pd+Cl- Si(OEt)3
13C NMR of the complex [(C3H5)Pd(2e)Cl]
H
FePh2P
NO
Pd+Cl- Si(OEt)3
23
31P NMR of the complex [(C3H5)Pd(2e)Cl]
H
FePh2P
NO
Pd+Cl-
H
Si(OEt)3
1H NMR f th l [(C H )Pd(2f)Cl]1H NMR of the complex [(C3H5)Pd(2f)Cl]
N
FePPh2
24
13C NMR of the complex [(C3H5)Pd(2f)Cl]
N
FePPh2
N
31P NMR of the complex [(C3H5)Pd(2f)Cl]
N
FePPh2
N
25
1H NMR of the complex [(C3H5)Pd(2g)Cl]Cl-
Ph2P NPd+
Cl
HSi(OEt)3
Fe
13C NMR of the complex [(C3H5)Pd(2g)Cl]
Pd+Cl-
Ph2P NPd+
HSi(OEt)3
Fe
26
31P NMR of the complex [(C3H5)Pd(2g)Cl]
Pd+Cl-
Ph2P NPd+
HSi(OEt)3
Fe
1H NMR of the complex [(C3H5)Pd(2g)Cl]
FePh2P
NO
Pd+Cl-
H
Si(OEt)3Fe
27
1H NMR of the complex [(C3H5)Pd(3d)Cl] in MeOH-d4
FePh2P
N
Pd+Cl-
H
Si(OEt)3Pd
PPh2
13C NMR of the complex [(C3H5)Pd(3d)Cl] in MeOH-d4
H
FePh2P
N
Pd+
P
Cl- Si(OEt)3
PPh2
28
31P NMR of the complex [(C3H5)Pd(3d)Cl] in MeOH-d4
N
H
FePh2P
N
Pd+
P
Cl- Si(OEt)3
PPh2
1H NMR of the complex [(C3H5)Pd(3d)Cl] in CDCl3
H
FePh2P
N
Pd+Cl- Si(OEt)3
PPh2
29
13C NMR of the complex [(C3H5)Pd(3d)Cl] in CDCl3H
FePh2P
N
Pd+
P
Cl- Si(OEt)3
PPh2
31P NMR of the complex [(C3H5)Pd(3d)Cl] in CDCl3N
H
FePh2P
Pd+
PPh2
Cl- Si(OEt)3
2
30
31P MAS-NMR of (R,S)-C3PPF
FPh2P
N
Pd+Cl-
SiO
OO
H
Fe 2 Pd Cl O
silica surface
31P MAS-NMR of (S,R)-C6PPFP MAS NMR of (S,R) C6PPF
Pd+Cl-
SiO
OO
Ph2P NPd
H
Fesilica
surface
31
31P MAS-NMR of (R,S)-COCPPFP MAS NMR of (R,S) COCPPF
H
FePh2P
NO
Pd+Cl-
SiO
OO
H
silica surface
31P MAS-NMR of(R,S)-2d/SiO2P MAS NMR of(R,S) 2d/SiO2
H
FePPh2
NSi
O
OO
silica surface
32
