Enantioselective Thiourea-Catalyzed Cationic Polycyclizations

被引:253
作者
Knowles, Robert R. [1 ]
Lin, Song [1 ]
Jacobsen, Eric N. [1 ]
机构
[1] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA
关键词
SQUALENE-HOPENE CYCLASE; PICTET-SPENGLER REACTIONS; PI-INTERACTIONS; AMINO-ACID; BIOMIMETIC CYCLIZATION; OXIDOSQUALENE CYCLASES; AROMATIC-HYDROCARBONS; POLYENE CYCLIZATION; FUNCTIONAL-ANALYSIS; ION-PAIR;
D O I
10.1021/ja101256v
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A new thiourea catalyst is reported for the enantioselective cationic polycyclization of hydroxylactams. Both the yield and enantioselectivity of this transformation were found to vary strongly with the identity of a single aromatic residue on a common catalyst framework, with more expansive and polarizable arenes proving optimal. Evidence is presented for a mechanism in which stabilizing cation-Pi interactions are a principal determinant of enantioselectivity.
引用
收藏
页码:5030 / +
页数:4
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