TY - JOUR
T1 - First total synthesis of modiolide A, based on the whole-cell yeast-catalyzed asymmetric reduction of a propargyl ketone
AU - Matsuda, Masaaki
AU - Yamazaki, Takahiro
AU - Fuhshuku, Ken ichi
AU - Sugai, Takeshi
N1 - Funding Information:
The authors thank Professor Jun-ichi Kobayashi of Hokkaido University for information on modiolide A, Professor Masatoshi Asami of Yokohama National University and Professor Keisuke Suzuki of Tokyo Institute of Technology for their valuable suggestions on the addition of TMS acetylide. Amano Enzyme Inc. is acknowledged with thanks for the gift of lipase PS-C. 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 - 2007/9/3
Y1 - 2007/9/3
N2 - While the first total synthesis of modiolide A (1a), a 10-membered ring lactone with a marine-origin was achieved, an important chiral building block for constructing the chirality at C-4 in 1a, (S)-6-[(4-methoxybenzyl)oxy]-1-trimethylsilyl-1-hexyn-3-ol (3a) was obtained in as high as 96.1% ee. Asymmetric reduction of a silylated propargyl ketone (5) mediated by whole-cell of Pichia minuta IAM 12215 was established. This yeast-mediated reduction was also applicable to provide stereochemically pure (3S,5R)-5-[(4-methoxybenzyl)oxy]-1-trimethylsilyl-1-hexyn-3-ol (15), a synthetic intermediate for the related 10-membered lactone, tuckolide (16).
AB - While the first total synthesis of modiolide A (1a), a 10-membered ring lactone with a marine-origin was achieved, an important chiral building block for constructing the chirality at C-4 in 1a, (S)-6-[(4-methoxybenzyl)oxy]-1-trimethylsilyl-1-hexyn-3-ol (3a) was obtained in as high as 96.1% ee. Asymmetric reduction of a silylated propargyl ketone (5) mediated by whole-cell of Pichia minuta IAM 12215 was established. This yeast-mediated reduction was also applicable to provide stereochemically pure (3S,5R)-5-[(4-methoxybenzyl)oxy]-1-trimethylsilyl-1-hexyn-3-ol (15), a synthetic intermediate for the related 10-membered lactone, tuckolide (16).
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U2 - 10.1016/j.tet.2007.06.038
DO - 10.1016/j.tet.2007.06.038
M3 - Article
AN - SCOPUS:34447633382
VL - 63
SP - 8752
EP - 8760
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 36
ER -
