π-アリルパラジウムとの反応における有機亜鉛の特異な反応挙動:カルボニル化による非対称ケトンの合成とπ-アリルパラジウムの極性転換反応
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概要
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Alkylorganozinc reagents, non-functionalized and functionalized with electrophilic functional groups, e.g., ester, ketone, nitrile, etc., display unique reactivity toward, π-allylpalladium complexes : They do not undergo usual coupling reaction, providing allylalkanes, instead, they form rather stable (reductive elimination resistant) alkylallylpalladium complexes, which either undergo a reductive carbonylative coupling reaction to provide alkyl allyl ketones under carbon monoxide (1 atm ; <I>unsymmetrical ketone synthesis via palladium catalyzed three-component coupling reaction of allylic benzoates, carbon monoxide, and alkylorganozincs</I>) or react further with another mole of organozinc reagents to furnish an equilibrium mixture with dialkylpalladium and allylzinc species (<I>umpolung of π-allylpalladium via transmetallation with organozincs</I>). Stereo-defined allylzincs, generated by this umpolung technique with inversion of configuration at the allylic center of allylic benozoates, react with aldehydes with high regio- and stereoselectivities. Mechanistic details of these unique reactions are discussed.
- 社団法人 有機合成化学協会の論文
- 1995-12-01