Metal-Free Reductive Cleavage of C-O σ-bonds in Acyloin Derivatives by an Organic Neutral Super-Electron-Donor
Metal-Free Reductive Cleavage of C-O σ-bonds in Acyloin Derivatives by an Organic Neutral Super-Electron-Donor
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DOI：
10.1021/jo901815t
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发表时间：
2009-11-20
影响因子：
3.6
通讯作者：
Murphy, John A.
中科院分区：
文献类型：
--
作者：
Cutulic, Sylvain P. Y.;Findlay, Neil J.;Murphy, John A.
中性有机电子给体7，正式形式为吡啶基二聚体，对丙环衍生物Ar(CO)CRR'OX （X = OAc, OPiv, OBz, OMs）中的C-O sigma键产生还原裂解作用，这是中性有机电子给体首次裂解C-O sigma键。该方法适用于大阵列的底物和减少对应物分离在良好到优异的产量。对于某些底物，供体7充当碱，影响与某些肌酰基蛋白的醋酸酯衍生物的缩合反应，生成丁烯内酯。对不同底物之间反应性的差异进行了理性化。
Neutral organic electron-donor 7, formally a pyridinylidene carbene dimer, effects reductive cleavage of C-O sigma-bonds in acyloin derivatives Ar(CO)CRR'OX (X = OAc, OPiv, OBz, OMs) and this represents the first cleavage of C-O sigma-bonds by a neutral organic electron-donor. The methodology is applicable to a large array of substrates and the reduced counterparts were isolated in good to excellent yields. For certain substrates, donor 7 behaves as a base, effecting condensation reactions with some acetate ester derivatives of acyloins, leading to butenolides. The variation in reactivity among the different substrates was rationalized.