Chemistry of substituted (2-butene-1,4-diyl)magnesium: a facile approach to complex carbocycles, functionalized ketones and alcohols, and silicon-containing heterocycles
作者:Reuben D. Rieke、Heping Xiong
DOI:10.1021/jo00009a034
日期:1991.4
Highly reactive magnesium reacts with a wide variety of substituted 1,3-dienes to give the corresponding substituted (2-butene-1,4-diyl)magnesium complexes. Reactions of symmetrical (2-butene-1,4-diyl)magnesium with alpha,omega-alkylene dihalides form three-, four-, five-, and six-membered carbocycles. Significantly, the cyclizations are always stereospecific and completely regioselective. Depending on the initial 1,3-diene and specific electrophiles, uncyclized products can be obtained. Stepwise reactions of (2,3-dimethyl-2-butene-1,4-diyl)magnesium with two different electrophiles afford polyfunctionalized ketones with the generation of a quaternary center. Formal 1,2-additions can be effected in this manner. Substituted five- and six-membered cyclic ketones can also be synthesized in one step by this approach. Treatment of unsymmetrical (2-butene-1,4-diyl)magnesium complexes with triorganosilyl chlorides followed by cyclohexanone results in additions across a terminal double bond with high regioselectivity. Silicon-containing heterocycles or spiro compounds can be readily synthesized by using the bis-Grignard reagents.