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000009771 0247_ $$2DOI$$a10.1002/ejoc.201000409
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000009771 084__ $$2WoS$$aChemistry, Organic
000009771 1001_ $$0P:(DE-HGF)0$$aScholz, R.$$b0
000009771 245__ $$aExperimental and Theoretical Study of the Enantiomerization Barrier of a-Sulfonyl Carbanions and Determination of the Structure of Lithium a-tert-blutylsulfonyl Carbanion Salts in Solution and the Crystal
000009771 260__ $$aWeinheim$$bWiley-VCH Verl.$$c2010
000009771 300__ $$a4559 - 4587
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000009771 440_0 $$01958$$aEuropean Journal of Organic Chemistry$$v2010$$x1434-193X$$y24
000009771 500__ $$aThis research was supported by the Deutsche Forschungsgemeinschaft (DFG), the Volkswagen Foundation, and Fonds der Chem'schen Industrie. We thank Professor Dr. H. Fritz and Dr. D. Hunkler for NMR measurements, Professor Dr. W. Bauer for cryoscopy measurements and valuable experimental advice, Dr. E. Keller for a version of SCHAKAL, and C. Vermeeren and D. Wolters for the preparation of the graphics. We are grateful to Professor Dr. H. J. Reich for his assistance in the analysis of the NMR spectra of the salt rac-9 in the presence of HMPA and for information concerning his unpublished results of a NMR spectroscopic study on the behaviour of lithium S-phenylsulfonyl carbanion salts towards H M PA.
000009771 520__ $$aDynamic NMR (DNMR) spectroscopy of [(RC)-C-1(R-2)SO2R3]Li (R-1, R-2 = alkyl, phenyl; R-3 = Ph, tBu, adamantyl, CEt3) in [D-8]THF has shown that the S-tBu, S-adamantyl, and S-CEt3 derivatives have a significantly higher enantiomerization barrier than their S-Ph analogues. C-alpha-S bond rotation is most likely the rate-determining step of the enantiomerization of the salts bearing a bulky group at the S atom and two substituents at the C-alpha, atom. Ab initio calculations on [Me(Ph)SO(2)tBu](-) gave information about the two C-alpha-S rotational barriers, which are dominated by steric effects. Cryoscopy of [(RC)-C-1(R-2)SO(2)tBu]Li in THF at -108 degrees C revealed the existence of monomers and dimers. X-ray crystal structure analysis of the monomers and dimers of [(RC)-C-1(R-2)SO(2)tBu]Li center dot L-n (R-1 = Me, Et, tBuCH(2), PhCH2, tBu; R-2 = Ph, L = THF, 12-crown-4, PMDTA) and [(RC)-C-1(R-2)SO2Ph]Li center dot 2diglyme [R-1 = R-2 = Me, Et; R-1-R-2 = (CH2)(5)] showed them to be O-Li contact ion pairs (CIPs). The monomers and dimers have a C-alpha-S conformation in which the lone-pair orbital at the C-alpha atom bisects the O-S-O angle and a significantly shortened C -S bond. The C-alpha atom of [(RC)-C-1(R-2)SO2R3]center dot L-n (R-1 = Ph; R-3 = Ph, tBu) is planar, whereas the C-alpha atom of [(RC)-C-1(R-2)SO2R3]Li center dot I., (R-1 = R-2 = alkyl) is strongly pyramidalized in the case of R-3 = Ph and most likely planar for R-3 = tBu. Ab initio calculations on [MeC(Me)SO2R](-) gave a pyramidalized C-alpha atom for R = Me and a nearly planar one for R = CF3 and tBu. The [(RC)-C-1(R-2)SO(2)tBu]Li salts were characterized by H-1, C-13, and Li-6 NMR spectroscopy.H-1{H-1} and Li-6{H-1} NOE experiments are in accordance with the existence of O-Li CIPs. H-1 and C-13 NMR spectroscopy of [(RC)-C-1(R-2)SO(2)tBu]Li in [D-8]THF at low temperatures showed equilibrium mixtures of up to five different species being most likely monomeric and dimeric O-Li CIPs with different configurations. According to Li-7 NMR spectroscopy, the addition of HMPA to [MeC(Ph)SO(2)tBu]Li in [D8ITHF at low temperatures causes the formation of the separated ion pair [MeC(Ph)SO(2)tBu]Li(HMPA)(4).
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000009771 650_7 $$2WoSType$$aJ
000009771 65320 $$2Author$$aCarbanions
000009771 65320 $$2Author$$aChirality
000009771 65320 $$2Author$$aEnantiomerization
000009771 65320 $$2Author$$aAb initio calculations
000009771 65320 $$2Author$$aCryoscopy
000009771 7001_ $$0P:(DE-HGF)0$$aHellmann, G.$$b1
000009771 7001_ $$0P:(DE-Juel1)129146$$aRohs, S.$$b2$$uFZJ
000009771 7001_ $$0P:(DE-HGF)0$$aRaabe, G.$$b3
000009771 7001_ $$0P:(DE-HGF)0$$aRaabe, G.$$b4
000009771 7001_ $$0P:(DE-HGF)0$$aRunsink, J.$$b5
000009771 7001_ $$0P:(DE-HGF)0$$aÖzdemir, D.$$b6
000009771 7001_ $$0P:(DE-HGF)0$$aLuche, O.$$b7
000009771 7001_ $$0P:(DE-HGF)0$$aHeß, T.$$b8
000009771 7001_ $$0P:(DE-HGF)0$$aGiesen, A.W.$$b9
000009771 7001_ $$0P:(DE-HGF)0$$aAtodiresei, J.$$b10
000009771 7001_ $$0P:(DE-HGF)0$$aLindner, H.J.$$b11
000009771 7001_ $$0P:(DE-HGF)0$$aGais, H.-J.$$b12
000009771 773__ $$0PERI:(DE-600)1475010-7$$a10.1002/ejoc.201000409$$gVol. 2010, p. 4559 - 4587$$p4559 - 4587$$q2010<4559 - 4587$$tEuropean journal of organic chemistry$$v2010$$x1434-193X$$y2010
000009771 8567_ $$uhttp://dx.doi.org/10.1002/ejoc.201000409
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