Formica Michele, Sorin Geoffroy, Farley Alistair J M, Díaz Jesús, Paton Robert S, Dixon Darren J
Department of Chemistry , Chemistry Research Laboratory , University of Oxford , Mansfield Road , Oxford OX1 3TA , UK . Email:
Faculté des Sciences Pharmaceutiques et Biologiques , Unité CNRS UMR 8638 COMETE , Paris Descartes University , Sorbonne Paris Cité , 4 Avenue de l'Observatoire , 75270 Paris Cedex 06 , France.
Chem Sci. 2018 Jul 23;9(34):6969-6974. doi: 10.1039/c8sc01804a. eCollection 2018 Sep 14.
The first enantioselective sulfa-Michael addition of alkyl thiols to alkenyl benzimidazoles, enabled by a bifunctional iminophosphorane (BIMP) organocatalyst, is described. The iminophosphorane moiety of the catalyst provides the required basicity to deprotonate the thiol nucleophile while the chiral scaffold and H-bond donor control facial selectivity. The reaction is broad in scope with respect to the thiol and benzimidazole reaction partners with the reaction proceeding in up to 98% yield and 96 : 4 er.
本文描述了在双功能亚胺基膦烷（BIMP）有机催化剂作用下，烷基硫醇对烯基苯并咪唑的首例对映选择性硫醚-迈克尔加成反应。催化剂的亚胺基膦烷部分提供了使硫醇亲核试剂去质子化所需的碱性，而手性骨架和氢键供体则控制着面选择性。该反应对于硫醇和苯并咪唑反应底物具有广泛的适用性，反应产率高达98%，对映体比例为96:4。
