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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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