Bidirectional synthesis of the central amino acid of chloptosin.
[reaction: see text] An efficient total synthesis of (2S,2'S,3aR,3'aR,8aR,8'aR)-6,6'-dichloro-3a,3'a-dihydroxy-1,1',2,2',3,3a,3',3'a,8,8a,8',8'a-dodecahydro-5,5'-bipyrrolo[2,3-b]indole-2,2'-dicarboxylic acid, the central amino acid component of chloptosin (1), is described. Starting from m-chloronitrobenzene, this C(2)-symmetrical amino acid was synthesized by using a 14-step route, in which a Zinin benzidine rearrangement, intramolecular Heck reaction, and selenocyclization and oxidative deselenation served as key steps. The absolute stereochemistry of the target was confirmed by X-ray single-crystal studies on a key intermediate (17).
Hong
Wen-Xu
WX
State Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, China.
Chen
Ling-Jun
LJ
Zhong
Chun-Long
CL
Yao
Zhu-Jun
ZJ
D000596:Amino Acids / Q000138:chemical synthesis*; D018360:Crystallography, X-Ray; D008968:Molecular Conformation; D015394:Molecular Structure; D010456:Peptides, Cyclic / Q000737:chemistry*; D011724:Pyridazines / Q000737:chemistry*; D013237:Stereoisomerism
D000596:Amino Acids; D010456:Peptides, Cyclic; D011724:Pyridazines; C414086:chloptosin