Nickel-catalyzed reductive coupling of alkynes and epoxides
Nickel-catalyzed reductive coupling of alkynes and epoxides
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DOI：
10.1021/ja0361401
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发表时间：
2003-07-09
影响因子：
15
通讯作者：
Jamison, TF
中科院分区：
文献类型：
--
作者：
Molinaro, C;Jamison, TF
镍催化的烯烃和环氧化物的分子内和分子间还原偶联提供了具有特定烯烃构型的合成有用的高烯丙醇。通常观察到非常高的区域选择性，环合反应对内环氧化物的开环具有完全的选择性。这一催化反应代表了在镍催化的多组分偶联反应中首次使用非π基电泳体，并且是第一种炔烃和环氧化物还原偶联的催化方法，对分子间和分子内的情况都有效，并且在机理上与这些情况不同，可能涉及镍(II)氧杂环烷。
Nickel-catalyzed, intramolecular and intermolecular reductive coupling of alkynes and epoxides affords synthetically useful homoallylic alcohols of defined alkene geometry. Very high regioselectivity is generally observed, and cyclizations proceed with complete selectivity for endo epoxide opening. This catalytic reaction represents the first use of a non-π-based electrophile in a growing class of nickel-catalyzed, multicomponent coupling reactions, and is the first catalytic method of reductive coupling of alkynes and epoxides that is effective for both intermolecular and intramolecular cases, and mechanistically distinct from these, possibly involving a nickella(II)oxetane.