对映选择性碳-硫键的形成：手性膦烯催化芳基硫醇对烯丙酸酯的γ-加成反应
Enantioselective Carbon-Sulfur Bond Formation: γ Additions of Aryl Thiols to Allenoates Catalyzed by a Chiral Phosphepine.
作者信息
Fujiwara Yuji, Sun Jianwei, Fu Gregory C
出版信息
Chem Sci. 2011;2:2196-2198. doi: 10.1039/c1sc00414j.
Abstract
An effective phosphine-catalyzed method has been developed for the enantioselective addition of aryl thiols to the γ position of allenoates, thereby furnishing ready access to aryl alkyl sulfides in very good ee. An array of mechanistic data are consistent with addition of the chiral phosphine to the allenoate being the turnover-limiting step of the catalytic cycle. The optimized reaction conditions, as well as the mechanistic observations, differ markedly from an earlier report on asymmetric additions of alkyl thiols to allenoates, which highlights the potential for divergent behavior between alkyl and aryl thiols when serving as nucleophiles.
摘要
已开发出一种有效的膦催化方法，用于将芳基硫醇对映选择性地加成到烯酸酯的γ位，从而能够以非常好的对映体过量（ee）方便地获得芳基烷基硫醚。一系列机理数据与手性膦加成到烯酸酯是催化循环的周转限制步骤相一致。优化的反应条件以及机理观察结果与早期关于烷基硫醇对烯酸酯的不对称加成的报道有显著差异，这突出了烷基硫醇和芳基硫醇作为亲核试剂时行为差异的可能性。
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