Thieme

Supporting Information for DOI: 10.1055/s-0036-1589023

© Georg Thieme Verlag KG Stuttgart · New York 2017

 

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SUPPORTING INFORMATION  

 

Synthesis and resolution of a chiral diamine: 2,2'‐(Propane‐2,2‐

diyl)dipyrrolidine 

 

Andreas F. Kotthausa, Frederic Ballaschka, Vjoni Stakaja, Fabian Mohra, Stefan F. Kirsch*,a 

 

a Bergische Universität Wuppertal, Gaußstr. 20, 42119 Wuppertal, Germany. 

Tableofcontent

Crystallographicdata S2

1Hand13CNMRspectraforallnewcompounds S8

ChiralHPLCtraces S14

 

   

 

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CrystallographicData

Crystalstructureofthe(S,S)‐6*2(R)‐mandelicacid;ellipsoidsaredrawnat30%probability.

Thecrystalstructureof(S,S)‐6*2(R)‐mandelicacidwasdepositedattheCambridgeCrystallographicDataCentre:CCDC1426294.

Table1Crystaldataandstructurerefinementfor

Identificationcode

Empiricalformula C27H38N2O6Formulaweight 486.59

Temperature/K 290

Crystalsystem trigonal

Spacegroup P31

a/Å 10.2465(4)

b/Å 10.2465(4)

c/Å 21.5589(7)

α/° 90.00

β/° 90.00

γ/° 120.00

Volume/Å3 1960.25(12)

Z 3

ρcalcmg/mm3 1.237

μ/mm‐1 0.087

F(000) 786.0

 

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Crystalsize/mm3 0.13×0.11×0.05

2Θrangefordatacollection 4.6to58.9°

Indexranges ‐12≤h≤12,‐12≤k≤14,‐28≤l≤28

Reflectionscollected 12533

Independentreflections 6012[R(int)=0.0296]

Data/restraints/parameters 6012/1/326

Goodness‐of‐fitonF2 1.048

FinalRindexes[I>=2σ(I)] R1=0.0524,wR2 =0.1111

FinalRindexes[alldata] R1=0.0765,wR2 =0.1257

Largestdiff.peak/hole/eÅ‐30.24/‐0.20

Flackparameter ‐0.7(10)

Table2FractionalAtomicCoordinates(×104)andEquivalentIsotropicDisplacementParameters(Å2×103)for.Ueqisdefinedas1/3ofofthetraceoftheorthogonalisedUIJtensor.

Atom x y z U(eq)

O1 8315(2) 3549(2) 4910.4(8) 51.7(4)

O2 9033(3) 3115(2) 4000.0(8) 66.3(6)

C12 9042(3) 3148(3) 4577.3(10) 39.8(5)

C14 9232(2) 1347(3) 5322.5(10) 37.8(5)

O3 10971(3) 2458(3) 4463.9(12) 74.3(7)

C19 8749(3) 1510(3) 5900.3(11) 44.5(5)

C13 10097(3) 2705(3) 4903.6(11) 43.3(5)

C15 8909(4) ‐76(3) 5138.4(12) 59.2(7)

C17 7634(4) ‐1130(4) 6092.4(14) 71.8(9)

C18 7946(3) 276(3) 6282.8(12) 57.1(7)

C16 8108(5) ‐1301(3) 5524.7(14) 79.1(10)

N1 5254(2) 2475(2) 4856.8(8) 36.6(4)

N2 4267(2) 3132(2) 7108.0(8) 36.3(4)

C5 4953(2) 2970(2) 5987.1(9) 32.5(4)

C4 4198(3) 2011(2) 5403.8(10) 38.7(5)

C8 3693(3) 2470(3) 6475.4(9) 39.0(5)

C1 4798(4) 1094(3) 4478.7(12) 58.7(7)

C11 3156(3) 3494(4) 7394.2(12) 58.6(7)

C6 6181(3) 2681(5) 6238.4(12) 68.5(9)

C7 5658(4) 4633(3) 5827.5(12) 64.1(8)

C9 2458(4) 2831(6) 6349.3(14) 100.6(15)

C3 3562(5) 314(3) 5454.4(15) 87.2(12)

C2 4207(6) ‐135(3) 4938.6(16) 97.5(14)

C10 1819(4) 2800(6) 6984.8(15) 93.8(13)

O4 4623(2) 4314(2) 4217.2(8) 52.1(4)

O5 6893(2) 6336(2) 4309.4(8) 56.3(5)

C20 5496(3) 5692(3) 4272.9(9) 40.2(5)

C21 4761(3) 6677(3) 4312.3(12) 48.0(6)

O6 3219(3) 5789(3) 4463.9(13) 76.7(7)

C22 5013(3) 7543(3) 3715.4(11) 44.0(5)

 

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C23 4038(4) 6956(4) 3223.8(14) 64.3(7)

C27 6280(4) 8964(3) 3650.5(14) 64.0(7)

C25 5546(5) 9196(5) 2635.0(17) 86.8(12)

C24 4301(5) 7784(6) 2677.2(15) 83.5(11)

C26 6543(5) 9774(4) 3117.6(17) 85.2(11)

Table3AnisotropicDisplacementParameters(Å2×103)for.TheAnisotropicdisplacementfactorexponenttakestheform:‐2π2[h2a*2U11+...+2hka×b×U12]

Atom U11 U22 U33 U23 U13 U12O1 50.4(10) 61.4(11) 52.1(9) 6.4(8) 3.3(8) 34.6(9)

O2 111.5(17) 72.1(13) 36.0(9) 1.2(9) ‐5.6(10) 61.4(13)

C12 45.6(13) 36.2(12) 35.1(11) 4.0(9) 0.6(10) 18.5(11)

C14 32.2(11) 42.7(13) 39.1(11) 4.3(10) ‐5.9(9) 19.1(10)

O3 70.2(15) 90.4(17) 81.7(16) 30.5(13) 36.5(13) 54.7(14)

C19 45.9(13) 45.6(14) 47.1(13) 2.7(11) ‐1.8(10) 26.7(12)

C13 34.1(12) 49.4(14) 45.3(12) 7.8(11) 5.5(10) 20.1(11)

C15 85(2) 55.1(17) 39.5(13) ‐3.7(12) ‐4.5(13) 36.5(16)

C17 89(2) 52.3(18) 56.7(17) 19.5(14) 1.6(15) 22.5(17)

C18 61.2(17) 65.5(18) 45.0(13) 13.4(13) 7.4(12) 32.1(15)

C16 120(3) 44.2(17) 62.3(18) 2.2(14) ‐4.6(19) 33.5(18)

N1 43.0(11) 33.8(10) 32.6(9) ‐0.3(8) 0.0(7) 18.9(8)

N2 35.1(10) 42(1) 32.4(9) 1.1(8) ‐1.8(7) 19.8(8)

C5 32.5(11) 33.8(11) 30.5(10) 3.8(8) ‐2.1(8) 16.0(9)

C4 38.6(12) 36.7(12) 36.3(11) ‐2.0(9) 3.7(9) 15.3(10)

C8 33.7(12) 46.0(13) 31.5(11) ‐4.6(9) ‐0.5(8) 15.6(10)

C1 74.8(19) 46.3(15) 50.3(14) ‐11.4(12) 5.7(14) 26.6(14)

C11 64.3(18) 81(2) 47.3(14) ‐10.9(13) ‐0.5(12) 48.5(17)

C6 58.8(17) 128(3) 45.1(14) 15.2(16) 7.4(13) 66(2)

C7 97(2) 35.8(13) 37.4(12) ‐1.5(10) ‐1.7(13) 16.5(15)

C9 69(2) 222(5) 47.4(16) ‐19(2) ‐10.6(15) 100(3)

C3 123(3) 34.3(15) 69.9(19) ‐0.9(14) 32(2) 13.8(18)

C2 168(4) 43.6(17) 68(2) ‐6.3(15) 24(2) 44(2)

C10 63(2) 180(4) 60.7(18) ‐28(2) ‐5.4(15) 77(3)

O4 62.2(11) 50.0(11) 52.2(10) 0.7(8) ‐5.2(8) 34.1(10)

O5 54.0(11) 64.7(12) 58.9(11) ‐0.9(9) 6.9(9) 36.2(10)

C20 53.1(15) 50.0(15) 26(1) 3.8(9) 6.7(10) 32.1(13)

C21 53.9(15) 52.5(15) 48.0(13) 4.4(11) 13.5(11) 34.2(13)

O6 65.3(14) 87.9(16) 91.7(17) 24.3(15) 39.1(13) 49.4(13)

C22 48.1(14) 48.5(14) 47.9(13) 2.9(11) 7.4(11) 33.5(12)

C23 57.2(18) 76(2) 68.5(18) ‐0.7(15) ‐6.5(14) 40.1(16)

C27 71(2) 53.8(17) 65.9(17) 3.1(14) 3.9(15) 30.7(16)

C25 127(3) 111(3) 66(2) 36(2) 30(2) 92(3)

C24 98(3) 130(4) 58.1(18) ‐2(2) ‐11.2(18) 84(3)

C26 115(3) 60(2) 81(2) 22.7(17) 24(2) 44(2)

 

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Table4BondLengthsfor.

AtomAtomLength/Å AtomAtomLength/Å

O1 C12 1.243(3) C5 C7 1.521(3)

O2 C12 1.245(3) C4 C3 1.525(4)

C12 C13 1.536(3) C8 C9 1.509(4)

C14 C19 1.381(3) C1 C2 1.475(4)

C14 C13 1.518(3) C11 C10 1.479(4)

C14 C15 1.381(4) C9 C10 1.512(4)

O3 C13 1.411(3) C3 C2 1.480(5)

C19 C18 1.384(4) O4 C20 1.243(3)

C15 C16 1.383(4) O5 C20 1.243(3)

C17 C18 1.373(4) C20 C21 1.535(3)

C17 C16 1.360(4) C21 O6 1.412(3)

N1 C4 1.508(3) C21 C22 1.510(4)

N1 C1 1.491(3) C22 C23 1.372(4)

N2 C8 1.506(3) C22 C27 1.391(4)

N2 C11 1.495(3) C23 C24 1.397(5)

C5 C4 1.544(3) C27 C26 1.363(4)

C5 C8 1.542(3) C25 C24 1.372(6)

C5 C6 1.528(3) C25 C26 1.368(6)

Table5BondAnglesfor.

AtomAtomAtom Angle/˚ AtomAtom Atom Angle/˚

O1 C12 O2 126.1(2) C3 C4 C5 117.4(2)

O1 C12 C13 117.4(2) N2 C8 C5 113.27(17)

O2 C12 C13 116.5(2) N2 C8 C9 103.9(2)

C19 C14 C13 120.4(2) C9 C8 C5 117.5(2)

C19 C14 C15 118.4(2) C2 C1 N1 104.1(2)

C15 C14 C13 121.2(2) C10 C11 N2 105.7(2)

C14 C19 C18 120.8(2) C8 C9 C10 103.8(2)

C14 C13 C12 111.67(18)C2 C3 C4 107.4(2)

O3 C13 C12 110.4(2) C1 C2 C3 107.2(3)

O3 C13 C14 111.5(2) C11 C10 C9 104.1(3)

C14 C15 C16 120.3(3) O4 C20 C21 116.2(2)

C16 C17 C18 119.6(3) O5 C20 O4 126.4(2)

C17 C18 C19 120.0(3) O5 C20 C21 117.4(2)

C17 C16 C15 120.9(3) O6 C21 C20 110.4(2)

C1 N1 C4 107.07(18)O6 C21 C22 112.6(2)

C11 N2 C8 108.11(16)C22 C21 C20 110.05(19)

C8 C5 C4 105.94(17)C23 C22 C21 121.8(2)

C6 C5 C4 111.4(2) C23 C22 C27 118.4(3)

C6 C5 C8 109.12(17)C27 C22 C21 119.8(2)

C7 C5 C4 109.55(17)C22 C23 C24 120.6(3)

C7 C5 C8 112.1(2) C26 C27 C22 121.3(3)

C7 C5 C6 108.8(2) C26 C25 C24 120.3(3)

N1 C4 C5 112.58(17)C25 C24 C23 119.4(3)

 

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N1 C4 C3 104.20(19)C27 C26 C25 120.0(4)

Table6HydrogenAtomCoordinates(Å×104)andIsotropicDisplacementParameters(Å2×103)for.

Atom x y z U(eq)

H19 8965 2461 6034 53

H13 10788 3554 5165 52

H15 9231 ‐210 4753 71

H17 7103 ‐1959 6350 86

H18 7618 399 6669 68

H16 7890 ‐2254 5394 95

H1A 5186 3176 4630 44

H1B 6212 2864 4987 44

H2A 4369 2467 7346 44

H2B 5173 3973 7075 44

H4 3364 2173 5289 46

H8 3214 1373 6515 47

H1C 4027 945 4180 70

H1D 5655 1160 4259 70

H11A 2892 3078 7809 70

H11B 3571 4576 7417 70

H6A 5731 1660 6383 103

H6B 6693 3359 6575 103

H6C 6889 2841 5915 103

H7A 6481 4914 5545 96

H7B 6022 5222 6199 96

H7C 4915 4812 5637 96

H9A 1695 2082 6079 121

H9B 2862 3817 6160 121

H3A 3837 67 5850 105

H3B 2472 ‐212 5424 105

H2C 5011 ‐291 5090 117

H2D 3437 ‐1066 4752 117

H10A 1303 3376 6989 113

H10B 1119 1774 7112 113

H21 5256 7409 4647 58

H23 3194 6000 3255 77

H27 6962 9369 3977 77

H25 5712 9763 2277 104

H24 3638 7381 2345 100

H26 7400 10720 3082 102

H3 10570(40) 2550(40) 4169(16) 71(12)

H6 2860(50) 5210(50) 4140(20) 103(16)

 

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Experimental

SinglecrystalsofC27H38N2O6[(S,S)‐6*2(R)‐mandelicacid]werepreparedbyrecrystallizationfromEtOH.AsuitablecrystalwasselectedandplacedonanOxfordDiffractionGeminiUltradiffractometer.Thecrystalwaskeptat290Kduringdatacollection.UsingOlex2,1thestructurewassolvedwiththeShelXS2structuresolutionprogramusingDirectMethodsandrefinedwiththeShelXL3refinementpackageusingLeastSquaresminimisation.

(1) Dolomanov,O.V.;Bourhis,L.J.;Gildea,R.J.;Howard,JudithA.K.;Puschmann,H.J.Appl.Cryst.2009,42,339.

(2) SHELXS,Sheldrick,G.M.ActaCryst.2008,A64,112.(3) SHELXL,Sheldrick,G.M.ActaCryst.2008,A64,112.

Crystalstructuredeterminationof(S,S)‐6*2(R)‐mandelicacid

CrystalDataforC27H38N2O6(M=486.59):trigonal,spacegroupP31(no.144),a=10.2465(4)Å,c=21.5589(7)Å,V=1960.25(12)Å3,Z=3,T=290K,μ(MoKα)=0.087mm‐1,Dcalc=1.237g/mm3,12533reflectionsmeasured(4.6≤2Θ≤58.9),6012unique(Rint=0.0296)whichwereusedinallcalculations.ThefinalR1was0.0524(>2sigma(I))andwR2was0.1257(alldata).

 

   

 

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1Hand13CNMRspectraforallnewcompounds

 

   

 

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