NAKATA Masya Dep. Applied Chemistry, Faculty of Science and Technology, Keio Univ,; Assist. P, 理工学部・応用化学科, 専任講師 (50118981)
TATSUTA Kuniaki Dep. Applied Chemistry, Faculty of Science and Technology, Keio Univ.; Prof., 理工学部・応用化学科, 教授 (40051627)
|Budget Amount *help
¥5,400,000 (Direct Cost: ¥5,400,000)
Fiscal Year 1987: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1986: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1985: ¥2,800,000 (Direct Cost: ¥2,800,000)
1. Total synthesis of elaiophylin: The antibiotic elaiophylin (1) has been first synthesized by a convergent route involving aldol coupling of (5R, 6R, 7R,)-5-0-(2-deoxy-3, 4-bis- 0-(isopropyldimethylsilyl)-<alpha>-L-fucopyranosyl)-6-ethyl-7-0-(diethylisopropylsilyl)-5, 7-dihydroxy- 3- octanone (2) and (7S, 8S, 15S, 16S: 3E, 5E, 11E, 13E)-8,16--bis-((1R)-1-formylethyl)-7,15-dimethyl-1, 9-dioxa- 3,5,11,13-cyclohexadecateteaene-2, 10-dione (3), followed by desylilation. The segments 2 and 3 were enantiospecifically synthesized from appropriate D-glucose derivative and 2-deoxy-L-fucose.
2. Synthesis of amphotericin B aglycon: The key segments 1 and 2 corresponding to the C_1-C_<20> and C_<21>-C_<37> portions of amphotericin B aglycon have been synthesized. The synthesis of 1 was accomplished by a convergent route involving coupling between the iodo compound (C_1-C_<12> segment) and the lithium compound generated from bis (dimethylthio) trimethylstannyl compound (C_<13>-C_<19> segment), intramolecular cycl-ic methyl acetalization, and (dimethoxyphosphinyl) methlation of C_<19>-methoxycarbonyl group. Both the C_1-C_<12> and C_<13>-C_<19> segments were stereoselectively synthesized from appropriate D-glucose derivatives. The unsaturated C_<21>-C_<37> segment was synthesized by the two-fold Horner-%emmons olefination with (2E, 4E)-6-( dimethoxyphosphinyl )-2, 4-hexadienoate of the C_<33>-C_<37> aldehydic segment which was enantiospecifically synthesized from appropriate D-glucose derivative.