Enantiodivergent synthesis of pyrrolo[2,1-α]isoquinolines based on diastereoselective Parham cyclization and α-amidoalkylation reactions

被引:48
作者
González-Temprano, I [1 ]
Osante, I [1 ]
Lete, E [1 ]
Sotomayor, N [1 ]
机构
[1] Univ Basque Country, Euskal Herriko Unibertsitatea, Fac Ciencias & Tecnol, Dept Quim Organ 2, E-48080 Bilbao, Spain
关键词
D O I
10.1021/jo049672o
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Enantiodivergent synthesis of C-10b-substituted pyrrolo[2,1-a]isoquinolines starting from an enantiomerically pure N-phenethylnorborn-5-en-endo-2,3-dicarboxyimide 3a, with a 2-exo-hydroxy10-bornylsulfinyl group as a chiral auxiliary, has been developed. The key transformations are derived from diastereoselective intramolecular cyclization of aryllithiums and alpha-amidoalkylation reactions, with the ethylidene bridge of the norbornene moiety dictating the stereochemical outcome in both types of reactions. Thus, the organolithium addition-intramolecular alpha-amidoalkylation. sequence on imide 3a afforded stereoselectively the R configuration at C-12b, whereas the tandem Parham cyclization-intermolecular alpha-amidoalkylation reactions on the corresponding iodinated imide 3b occurred with complete control of stereoselectivity, leading to the epimer at C-12b. Subsequent reductive removal of the chiral auxiliary and retro-Diels-Alder reaction afforded (10bS)and (10bR)-pyrroloisoquinolines 1 in high yields and optical purities (>99% ee).
引用
收藏
页码:3875 / 3885
页数:11
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