TY - JOUR
T1 - New chemo-enzymatic route toward N-acetylneuraminic acid derivatives with alkyl groups at C-7 hydroxyl group
AU - Calveras, Jordi
AU - Nagai, Yasuhito
AU - Sultana, Israt
AU - Ueda, Yuji
AU - Higashi, Toshinori
AU - Shoji, Mitsuru
AU - Sugai, Takeshi
N1 - Funding Information:
The authors thank Dr. Yoshihiko Hirose of Amano Enzyme Inc. for generous gift of lipase PS-IM and Dr. Yoichi Suzuki of Novozymes Japan for Novozym 435. J.C. thanks postdoctoral fellowship from the Japanese society for the promotion of science (No. P07435). This work was supported both by a Grant-in-Aid for Scientific Research 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 - 2010/6/12
Y1 - 2010/6/12
N2 - Based on chemo-enzymatic regio- and stereoselective reactions, new routes toward C-4 substituted N-acetyl-d-mannosamine (ManNAc) and the corresponding sialic acids from d-glucal were established. Lipase-catalyzed regioselective transformation of d-glucal and related substrates furnished precursors on which carbamate and alkyl substituent were properly introduced at C-3 and at C-4, respectively. Cyclic carbamate formation through rhodium-nitrenoid intermediates with iodobenzene pivalate and tert-butyl alcohol proceeded in manno-configured at C-2 as well as α- at C-1, exclusively. Ring opening and deprotection under mild conditions furnished the target ManNAc derivatives, which were the substrates for aldolase-catalyzed reactions.
AB - Based on chemo-enzymatic regio- and stereoselective reactions, new routes toward C-4 substituted N-acetyl-d-mannosamine (ManNAc) and the corresponding sialic acids from d-glucal were established. Lipase-catalyzed regioselective transformation of d-glucal and related substrates furnished precursors on which carbamate and alkyl substituent were properly introduced at C-3 and at C-4, respectively. Cyclic carbamate formation through rhodium-nitrenoid intermediates with iodobenzene pivalate and tert-butyl alcohol proceeded in manno-configured at C-2 as well as α- at C-1, exclusively. Ring opening and deprotection under mild conditions furnished the target ManNAc derivatives, which were the substrates for aldolase-catalyzed reactions.
UR - http://www.scopus.com/inward/record.url?scp=77953590937&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=77953590937&partnerID=8YFLogxK
U2 - 10.1016/j.tet.2010.04.045
DO - 10.1016/j.tet.2010.04.045
M3 - Article
AN - SCOPUS:77953590937
VL - 66
SP - 4284
EP - 4291
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 24
ER -