Total synthesis of siomycin A: construction of synthetic segments.
The five practical segments for the total synthesis of siomycin A, that is, the dehydropiperidine segment A (5), the pentapeptide segment B (3), the dihydroquinoline segment C (6), and the beta-phenylselenoalanine dipeptide segments D (7) and E (4), were synthesized. Segment A (5) was constructed by the coupling of the azomethine ylide and the chiral sulfinimine, followed by the stereoselective reduction of the six-membered imine function. Segment B (3) was synthesized by the phenylselenylation of the beta-lactone, stereoselective vinylzinc addition to the chiral sulfinimine, and oxazoline-thioamide conversion. Segment C (6) was prepared by the one-pot olefination of the tetrahydroquinoline N-oxide using triflic anhydride and triethylamine, stereoselective reduction of the methyl ketone function, and regioselective Yb(OTf)(3)-catalyzed epoxide opening by the amino group. Segments D (7) and E (4) were synthesized by coupling of the properly protected beta-phenylselenoalanines.
Mori
Tomonori
T
Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
Higashibayashi
Shuhei
S
Goto
Taiji
T
Kohno
Mitsunori
M
Satouchi
Yukiko
Y
Shinko
Kazuyuki
K
Suzuki
Kengo
K
Suzuki
Shunya
S
Tohmiya
Hiraku
H
Hashimoto
Kimiko
K
Nakata
Masaya
M
D000475:Alkenes / Q000737:chemistry; D000900:Anti-Bacterial Agents / Q000138:chemical synthesis / Q000737:chemistry; D018360:Crystallography, X-Ray; D006873:Hydroquinones / Q000737:chemistry; D007097:Imines / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D010455:Peptides / Q000138:chemical synthesis* / Q000737:chemistry; D011759:Pyrrolidines / Q000737:chemistry; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry; D013452:Sulfonium Compounds / Q000737:chemistry
D000475:Alkenes; D000900:Anti-Bacterial Agents; D006873:Hydroquinones; D007097:Imines; D010455:Peptides; D011759:Pyrrolidines; D013438:Sulfhydryl Compounds; D013452:Sulfonium Compounds; C522016:sulfinimine; C024711:siomycin A; C031927:hydroquinone