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Homogeneous [Ru III (Me 3 tacn)Cl 3 ]‐Catalyzed Alkene cis ‐Dihydroxylation with Aqueous Hydrogen Peroxide
Author(s) -
Yip WingPing,
Ho ChiMing,
Zhu Nianyong,
Lau TaiChu,
Che ChiMing
Publication year - 2008
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200700237
Subject(s) - chemistry , dihydroxylation , alkene , catalysis , hydrogen peroxide , cyclooctene , aqueous solution , cyclopentene , yield (engineering) , cycloheptene , organic chemistry , medicinal chemistry , enantioselective synthesis , materials science , metallurgy
A simple and green method that uses [Ru(Me 3 tacn)Cl 3 ] ( 1 ; Me 3 tacn= N , N ′, N ′′‐trimethyl‐1,4,7‐triazacyclononane) as catalyst, aqueous H 2 O 2 as the terminal oxidant, and Al 2 O 3 and NaCl as additives is effective in the cis ‐dihydroxylation of alkenes in aqueous tert ‐butanol. Unfunctionalized alkenes, including cycloalkenes, aliphatic alkenes, and styrenes (14 examples) were selectively oxidized to their corresponding cis ‐diols in good to excellent yield (70–96 %) based on substrate conversions of up to 100 %. The preparation of cis ‐1,2‐cycloheptanediol (119 g, 91 % yield) and cis ‐1,2‐cyclooctanediol (128 g, 92 % yield) from cycloheptene and cyclooctene, respectively, on the 1‐mol scale can be achieved by scaling up the reaction without modification. Results from Hammett correlation studies on the competitive oxidation of para ‐substituted styrenes ( ρ =−0.97, R =0.988) and the detection of the cycloadduct [(Me 3 tacn)ClRuHO 2 (C 8 H 14 )] + by ESI‐MS for the 1 ‐catalyzed oxidation of cyclooctene to cis ‐1,2‐cyclooctanediol are similar to those of the stoichiometric oxidation of alkenes by cis ‐[(Me 3 tacn)(CF 3 CO 2 )Ru VI O 2 ] + through [3+2] cycloaddition (W.‐P. Yip, W.‐Y. Yu, N. Zhu, C.‐M. Che, J. Am. Chem. Soc. 2005 , 127 , 14239).