On the Additions of Lithium Methyl p-Tolyl Sulfoxide to N-(PMP)Arylaldimines 英文参考文献.docVIP

Molecules 2001, 6, 424–432 molecules ISSN 1420-3049 On the Additions of Lithium Methyl p-Tolyl Sulfoxide to N- (PMP)Arylaldimines Cristina Zucca,1 Pierfrancesco Bravo,1,2 Eleonora Corradi,1 Stefano V. Meille,1 Alessandro Volonterio,2 and Matteo Zanda1,* 1 Dipartimento di Chimica del Politecnico di Milano, via Mancinelli 7, I-20131 Milano, Italy. Tel. +39 (02) Fax +39 (02) 2 C.N.R. - Centro di Studio sulle Sostanze Organiche Naturali, via Mancinelli 7, I-20131 Milano, Italy * Author to whom correspondence should be addressed; e-mail zanda@dept.chem.polimi.it Received: 8 March 2001; in revised form 3 April 2001 / Accepted: 4 April 2001 / Published: 30 April 2001 Abstract: The results presented in this paper confirm that the stereochemical outcome of the reversible additions of lithium (R)-methyl p-tolyl sulfoxide to N-arylidene-p-anisidines (N- PMP imines) depends on: (a) the reaction conditions used and (b) the electronic properties of the arylidene moiety on the starting imine. In particular, we show that under kinetic control (-70 °C) the additions involving electron-rich N-arylidene groups occur with very high stereocontrol in favor of the (2S,RS)-diastereomers, whereas an electron-deficient group favors the opposite stereochemical outcome. Based on the observations above, a mechanistic hypothesis is proposed. Keywords: Sulfoxides, asymmetric synthesis, imines. Introduction Additions of chiral lithium sulfoxides to imines represent a powerful tool in asymmetric synthesis [1]. We have recently reported that kinetically controlled additions (-70 °C) of lithium methyl p-tolyl sulfoxide (2) (Scheme 1) to N-PMP(imines) (PMP = p-methoxyphenyl) derived from a series of aromatic aldehydes having a variable degree of fluorination occur with a progressively higher stereocontrol in favor of (2S,RS)-β-aminosulfoxides 3 with decreasing the number of fluorine atoms on the N-arylidene groups [