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Synthesis and Stereochemical Assignment of Crypto‐Optically Active 2 H 6 ‐Neopentane
Author(s) -
Masarwa Ahmad,
Gerbig Dennis,
Oskar Liron,
Loewenstein Aharon,
Reisenauer Hans Peter,
Lesot Philippe,
Schreiner Peter R.,
Marek Ilan
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201505349
Subject(s) - neopentane , enantiomer , spectroscopy , absolute configuration , vibrational circular dichroism , circular dichroism , chemistry , nuclear magnetic resonance spectroscopy , chiral column chromatography , chirality (physics) , molecule , density functional theory , deuterium , enantioselective synthesis , crystallography , stereochemistry , computational chemistry , organic chemistry , chiral symmetry , physics , atomic physics , catalysis , nambu–jona lasinio model , quantum mechanics , quark
The determination of the absolute configuration of chiral molecules is at the heart of asymmetric synthesis. Here we probe the spectroscopic limits for chiral discrimination with NMR spectroscopy in chiral aligned media and with vibrational circular dichroism spectroscopy of the sixfold‐deuterated chiral neopentane. The study of this compound presents formidable challenges since its stereogenicity is only due to small mass differences. For this purpose, we selectively prepared both enantiomers of 2 H 6 ‐ 1 through a concise synthesis utilizing multifunctional intermediates. While NMR spectroscopy in chiral aligned media could be used to characterize the precursors to 2 H 6 ‐ 1 , the final assignment could only be accomplished with VCD spectroscopy, despite the fleetingly small dichroic properties of 1 . Both enantiomers were assigned by matching the VCD spectra with those computed with density functional theory.