Drabowicz J, Dudziński B, Mikołajczyk M, Wang F, Dehlavi A, Goring J, Park M, Rizzo C J, Polavarapu P L, Biscarini P, Wieczorek M W, Majzner W R
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, 90-363 Lódz, Sienkiewicza 112, Poland.
J Org Chem. 2001 Feb 23;66(4):1122-9. doi: 10.1021/jo0011179.
Alkylation of the alpha-carbanion of (R)-(-)-tert-butyl methyl sulfoxide (4) with n-propyl bromide afforded (+)-n-butyl tert-butyl sulfoxide (1) to which the absolute configuration (R) was ascribed. This assignment was confirmed by X-ray analysis of the complex 6 obtained from the enantiomerically pure sulfoxide (-)-1 and mercury chloride. Vibrational absorption and circular dichroism spectra of (+)-1 were measured in CDCl3 solution in the 2000-900 cm(-1) region and compared with the ab initio predictions of absorption and VCD spectra obtained with density functional theory using the B3LYP/6-31G basis set for different conformers of (R)-1. This comparison indicated also that (+)-1 is of the (R)-configuration.
(R)-(-)-叔丁基甲基亚砜(4)的α-碳负离子与正丙基溴发生烷基化反应，得到(+)-正丁基叔丁基亚砜(1)，其绝对构型被指定为(R)。通过对由对映体纯的亚砜(-)-1和氯化汞得到的配合物6进行X射线分析，证实了这一构型指定。在CDCl₃溶液中，于2000 - 900 cm⁻¹区域测量了(+)-1的振动吸收光谱和圆二色光谱，并与使用密度泛函理论、B3LYP/6 - 31G基组对(R)-1的不同构象得到的吸收光谱和VCD光谱的从头算预测结果进行了比较。这种比较也表明(+)-1具有(R)构型。
