TY - JOUR
T1 - Lipase-catalyzed enantio- and regioselective transformation of 3-epi-shikimic acid derivatives as the key step for the entry of polyoxygenated carbacycles
AU - Hamada, Manabu
AU - Higashi, Toshinori
AU - Shoji, Mitsuru
AU - Umezawa, Kazuo
AU - Sugai, Takeshi
N1 - Funding Information:
The authors thank Dr. Yoichi Suzuki of Novozymes Japan for generous gift of Novozym 435. This work was supported both by a Grant-in-Aid for Scientific Research (No.18580106) and “’High-Tech Research Center” Project for Private Universities: matching fund subsidy 2006-2011 from the Ministry of Education, Culture, Sports, Science and Technology, Japan, and acknowledged with thanks.
PY - 2010/11
Y1 - 2010/11
N2 - Candida antarctica lipase B (Novozym 435)-catalyzed transesterification on methyl (±)-3,4-di-O-acetyl-5-O-(tert-butyldimethyl)silyl-3-epi-shikimate worked highly regio- and enantioselective manner. Only (3R,4S,5S)-isomer reacted with an E value over 500, exclusively on C-3 acetate. The regio- and enantioselectivity were greatly affected by the substitution pattern on the hydroxy groups. Towards polyoxygenated carbacycles, the above-mentioned highly selective transformation enabled the subsequent stereoselective inversion and dihydroxylation, to give methyl (3S,4R,5S)-3,4,5-triacetoxy-1- cyclohexenecarboxylate [antipode of naturally occurring methyl (-)-3,4,5-tri-O-acetylshikimate], and methyl (1R,2S,3S,4R,5R)-3,4-diacetoxy-5- (tert-butyldimethyl)silyloxy-1,2-dihydroxy-cyclohexanecarboxylate.
AB - Candida antarctica lipase B (Novozym 435)-catalyzed transesterification on methyl (±)-3,4-di-O-acetyl-5-O-(tert-butyldimethyl)silyl-3-epi-shikimate worked highly regio- and enantioselective manner. Only (3R,4S,5S)-isomer reacted with an E value over 500, exclusively on C-3 acetate. The regio- and enantioselectivity were greatly affected by the substitution pattern on the hydroxy groups. Towards polyoxygenated carbacycles, the above-mentioned highly selective transformation enabled the subsequent stereoselective inversion and dihydroxylation, to give methyl (3S,4R,5S)-3,4,5-triacetoxy-1- cyclohexenecarboxylate [antipode of naturally occurring methyl (-)-3,4,5-tri-O-acetylshikimate], and methyl (1R,2S,3S,4R,5R)-3,4-diacetoxy-5- (tert-butyldimethyl)silyloxy-1,2-dihydroxy-cyclohexanecarboxylate.
KW - Kinetic resolution
KW - Lipase
KW - Regioselective transformation
KW - Transesterification
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U2 - 10.1016/j.molcatb.2010.07.009
DO - 10.1016/j.molcatb.2010.07.009
M3 - Article
AN - SCOPUS:77956910133
SN - 1381-1177
VL - 67
SP - 78
EP - 84
JO - Journal of Molecular Catalysis - B Enzymatic
JF - Journal of Molecular Catalysis - B Enzymatic
IS - 1-2
ER -