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Enantioselective Heck–Matsuda Arylations through Chiral Anion Phase‐Transfer of Aryl Diazonium Salts
Author(s) -
Avila Carolina M.,
Patel Jigar S.,
Reddi Yernaidu,
Saito Masato,
Nelson Hosea M.,
Shunatona Hunter P.,
Sigman Matthew S.,
Sunoj Raghavan B.,
Toste F. Dean
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201702107
Subject(s) - chemistry , enantioselective synthesis , aryl , cyclopentene , catalysis , isomerization , alkene , phosphoric acid , cycloheptene , organic chemistry , combinatorial chemistry , alkyl
A mild, asymmetric Heck–Matsuda reaction of five‐, six‐ and seven‐membered ring alkenes and aryl diazonium salts is presented. High yields and enantioselectivities were achieved using Pd 0 and chiral anion co‐catalysts, the latter functioning as a chiral anion phase‐transfer (CAPT) reagent. For certain substrate classes, the chiral anion catalysts were modulated to minimize the formation of undesired by‐products. More specifically, BINAM‐derived phosphoric acid catalysts were shown to prevent alkene isomerization in cyclopentene and cycloheptene starting materials. DFT(B3LYP‐D3) computations revealed that increased product selectivity resulted from a chiral anion dependent lowering of the activation barrier for the desired pathway.