Highly Selective Addition of a Broad Spectrum of Trimethylsilane Pro‐nucleophiles to N‐tert‐Butanesulfinyl Imines

Abstract

Addition of organotrimethylsilane reagents to chiral N-tert-butanesulfinyl imines can be achieved in good yields and with excellent diastereoselectivities by employing TMSO(-)/Bu4N(+) as a Lewis base activator in THF. A variety of aliphatic, aromatic, heteroaromatic and organometallic chiral imines were utilised as electrophiles for the synthesis of enantioenriched N-tert-butanesulfinyl amides. Remarkably, the same sets of reaction conditions could be used with a highly diverse range of bench-stable organotrimethylsilane reagents, which highlights the generality and robustness of this methodology.

Synthesis of α‐Ethynyl Glycines

“…[44] As a result, α-alkynyl glycine derivative 59 was produced in moderate yield and good diastereoselectvity. Zanda's group performed the synthesis of enantiomerically pure α-ethynyl trifluoroalanine ester (S)-64 by using the stereoselective addition of ethynylmagnesium bromide to N-tolylsulfinimine ester 62 (Scheme 17).…”

One-pot aminobenzylation of aldehydes with toluenes

“…2g ), and Grignard reagents (Fig. 2h ) to in situ generated N -(trimethylsilyl)imines were developed by Giles 31 and Hart 32 , 33 , respectively.…”

C‐Silyl‐N,N‐dialkyl‐N′‐arylformamidines: Synthesis and Reactions with Phosphorus(III) Chlorides

“…The absence of methods for the C ‐functionalization of N , N ‐dialkyl‐ N′ ‐arylformamidines and our expertise in the synthesis of C ‐phosphanyl‐ N , N ‐dialkyl‐ N′ ‐arylformamidines prompted us to attempt the synthesis of C ‐silyl‐ N , N ‐dialkyl‐ N′ ‐arylformamidines. Analogous known (trimethylsilyl)‐substituted heteroaromatic compounds are susceptible to facile electrophilic cleavage of the C–Si bond and, thus, were extensively used in reactions with various electrophiles …”