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Total Synthesis of Siomycin A: Construction of Synthetic Segments
Author(s) -
Mori Tomonori,
Higashibayashi Shuhei,
Goto Taiji,
Kohno Mitsunori,
Satouchi Yukiko,
Shinko Kazuyuki,
Suzuki Kengo,
Suzuki Shunya,
Tohmiya Hiraku,
Hashimoto Kimiko,
Nakata Masaya
Publication year - 2008
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200800032
Subject(s) - stereoselectivity , imine , epoxide , triethylamine , regioselectivity , ketone , stereochemistry , total synthesis , chemistry , racemization , organic chemistry , catalysis
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 β‐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 β‐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 β‐phenylselenoalanines.