Water-Accelerated Organometallic Chemistry: Alkyne Carboalumination – Sulfinimine Addition and Asymmetric Synthesis of Allylic Amines

Abstract

Dedicated to Professor Dieter Seebach on the occasion of his 65th birthday Carboalumination of alkynes in the presence of catalytic Cp 2 ZrCl 2 and H 2 O affords vinyl-alane intermediates, which serve as nucleophiles in the subsequent addition to enantiomerically enriched (tertbutyl)-and (para-tolyl)sulfinimines. This new in situ protocol produces two new CÀC bonds. Chiral allylic sulfinamides are obtained in high diastereoselectivity and in good yield. Cleavage of the chiral auxiliary leads to synthetically useful allylic amine building blocks, and facile oxidative degradation of the alkene moiety can be used as an approach toward amino acid derivatives and for assignment of absolute configuration.

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update

“…Carboalumination of alkynes in the presence of catalytic Cp 2 ZrCl 2 and H 2 O affords vinylalane intermediates, which serve as nucleophiles in the subsequent addition to generate enantiomerically enriched ( tert -butyl)- and ( p -tolyl)sulfinimines. Chiral allylic sulfinamides are obtained in high diastereoselectivity and in good yield

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Decreased abundance of trefoil factor 1 transcript in the majority of gastric carcinomas

“…To date, modern methods used to prepare trisubstituted allylic alcohols are alkyne hydrometalation or carbometalation, mediated by stoichiometric organometallic reagents 15–17. In a similar fashion, allylic amines are accessible by use of imines are used as the electrophile instead of aldehydes 18. Most of these methods only warrant regioselectivity in the metalation step for selected examples and, thus, the product range of trisubstituted allylic alcohols and amines is limited.…”

Stereoselective Synthesis of α‐Branched Amines by Nucleophilic Addition of Unstabilized Carbanions to Imines

“…As seen in Scheme 1.14, exceptions to this are when benzyl- [50], allylmagnesium chloride [51], vinylaluminum [52,53], or vinylcopper reagents are used as nucleophiles [54].…”