Asymmetric synthesis of neolignans (-)-epi-conocarpan and (+)-conocarpan via Rh(II)-catalyzed C-H insertion process and revision of the absolute configuration of (-)-epi-conocarpan.
Catalytic asymmetric synthesis of neolignan natural products (-)-epi-conocarpan and (+)-conocarpan has been achieved by exploiting an enantio- and diastereoselective intramolecular C-H insertion reaction to construct a cis-2-aryl-2,3-dihydrobenzofuran ring system as a key step. The C-H insertion reaction of 5-bromoaryldiazoacetate catalyzed by Rh(2)(S-PTTEA)(4), a new dirhodium(II) carboxylate complex that incorporates N-phthaloyl-(S)-triethylalaninate as chiral bridging ligands, provided 2-aryl-5-bromo-3-methoxycarbonyl-2,3-dihydrobenzofuran with exceptionally high diastereoselectivity (cis/trans = 97:3) and high enantioselectivity for the cis isomer (84% ee).
Natori
Yoshihiro
Y
Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan.
Tsutsui
Hideyuki
H
Sato
Naoki
N
Nakamura
Seiichi
S
Nambu
Hisanori
H
Shiro
Motoo
M
Hashimoto
Shunichi
S
D001572:Benzofurans / Q000138:chemical synthesis*; D002384:Catalysis; D017705:Lignans / Q000138:chemical synthesis*; D015394:Molecular Structure; D012238:Rhodium; D013237:Stereoisomerism
D001572:Benzofurans; D017705:Lignans; C447284:conocarpan; D012238:Rhodium