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Osmium‐Catalyzed Olefin Dihydroxylation and Aminohydroxylation in the Second Catalytic Cycle
Author(s) -
Wu Peng,
Hilgraf Robert,
Fokin Valery V.
Publication year - 2006
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.200505252
Subject(s) - dihydroxylation , chemistry , olefin fiber , catalysis , catalytic cycle , hydroxylation , osmium , chemoselectivity , organic chemistry , chelation , combinatorial chemistry , enantioselective synthesis , ruthenium , enzyme
Two catalytic cycles operate in the osmium‐catalyzed olefin dihydroxylation and aminohydroxylation. Slow hydrolysis of the Os(VI) monoglycolate (or monoazaglycolate in aminohydroxylation) intermediate often results in the addition of another molecule of olefin thereby shunting the catalysis into the second catalytic cycle. As a result, both enantio‐ and chemoselectivity are reduced. A series of new chelating ligands were devised, which force the catalysis into the second cycle while maintaining enantiocontrol in the olefin addition step. Excellent catalytic turnover and moderate to good enantioselectivity were achieved.