title: Chiral sulfur compounds studied by Raman optical activity: tert-butanesulfinamide and its precursor tert-butyl tert-butanethiosulfinate.
abstract: Two chiral sulfur compounds, tert-butyl tert-butanethiosulfinate (1) and tert-butanesulfinamide (2), with inversion of configuration, have been studied by Raman optical activity (ROA) and electronic circular dichroism combined with density functional theory calculation. With the S-S linkage in 1, the couplings between the two tertiary carbon atoms often generate large ROA signals, whereas the tertiary carbon atom itself generally makes a large contribution to ROA signals in 2 for similar vibrational modes. The conformational dependence of ROA parameters provides probing conformation around the S-S bond from a new perspective. The simultaneous use of electronic circular dichroism and ROA is warranted to extract reliable conformational information. ROA provides a suitable candidate for the stereochemical study of chiral sulfur compounds, especially its capability of sensing the conformation around the S-S bond.
authors.affiliation: State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China.
authors.forename: Shi
authors.initials: S
authors.lastname: Qiu
authors.forename: Guanna
authors.initials: G
authors.lastname: Li
authors.forename: Shengmei
authors.initials: S
authors.lastname: Lu
authors.forename: Baokun
authors.initials: B
authors.lastname: Huang
authors.forename: Zhaochi
authors.initials: Z
authors.lastname: Feng
authors.forename: Can
authors.initials: C
authors.lastname: Li