A stereoselective transformation of α,β-epoxyketones into alkenylphosphates having a hydroxymethyl group on the β-carbon was established by utilizing the [1,2]-phospha-Brook rearrangement under Brønsted base catalysis. The reaction involves the catalytic generation of an α-oxygenated carbanion located at the α-position of an epoxide moiety through the [1,2]-phospha-Brook rearrangement and the following epoxide opening. Further transformation of the alkenylphosphates by the palladium-catalyzed cross-coupling reaction with Grignard reagents provided allylic alcohols having a stereodefined all-carbon tetrasubstituted alkene moiety.

中文翻译：

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布朗斯台德碱催化的α，β-环氧酮的转化利用[1,2]-磷酸-布鲁克重排合成具有四取代烯烃部分的烯丙醇。

通过在布朗斯台德碱催化下利用[1,2]-磷-布鲁克重排，将α，β-环氧酮立体选择性转化为在β-碳上具有羟甲基的烯基磷酸酯。该反应包括通过[1,2]-磷-布鲁克重排和随后的环氧化物开环催化生成位于环氧化物部分的α-位的α-氧化的碳负离子。通过与格氏试剂的钯催化的交叉偶联反应进一步转化烯基磷酸酯，提供了具有立体定义的全碳四取代烯烃部分的烯丙基醇。