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Non‐Covalent Substrate Directed Enantioselective Heck Desymmetrization of cis ‐Cyclohex‐4‐ene‐1,2‐diol: Synthesis of all cis Chiral 5‐Aryl‐cyclohex‐3‐ene‐1,2‐diols and Mechanistic Investigation
Author(s) -
Angnes Ricardo A.,
Thompson Lee M.,
Mashuta Mark S.,
Correia Carlos R. D.,
Hammond Gerald B.
Publication year - 2018
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201800785
Subject(s) - desymmetrization , enantioselective synthesis , chemistry , heck reaction , ene reaction , diol , substrate (aquarium) , allylic rearrangement , stereochemistry , aryl , combinatorial chemistry , organic chemistry , catalysis , alkyl , oceanography , geology
Enantioselective substrate directed Heck reactions are desirable for the stereoselective synthesis of complex molecules. However, due to the coordination requirements of both chiral ligands and directing groups, such methodologies are underdeveloped. We report herein the desymmetrization of meso (1 R ,2 S )‐cyclohex‐4‐ene‐1,2‐diol in an enantioselective and substrate directed fashion. The method provides all cis substituted highly functionalized chiral allylic alcohols in a complementary fashion to other Heck protocols.The products were obtained in high enantioselectivities (higher than 95% ee) and moderate to high yields (38–87%). The noncovalent interactions responsible for the directing effect were elucidated through computational examination of relevant minima and transition structures.