Catalytic asymmetric synthesis of the endo-6-aryl-8-oxabicyclo[3.2.1]oct-3-en-2-one natural product from Ligusticum chuanxing via 1,3-dipolar cycloaddition of a formyl-derived carbonyl ylide using Rh2(S-TCPTTL)4.
The reaction of a six-membered cyclic formyl-carbonyl ylide derived from alpha-diazo-beta-ketoester with phenylacetylene derivatives under the catalysis of dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], Rh(2)(S-TCPTTL)(4), provides cycloadducts containing an 8-oxabicyclo[3.2.1]octane ring system in up to 97% ee. This represents the first example of an enantioselective 1,3-dipolar cycloaddition of a cyclic formyl-carbonyl ylide. Using this catalytic process, an asymmetric synthesis of endo-6-aryl-8-oxabicyclo[3.2.1]oct-3-en-2-one natural product 1 from Ligusticum chuanxing Hort. has been achieved.
Shimada
Naoyuki
N
Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan.
Hanari
Taiki
T
Kurosaki
Yasunobu
Y
Takeda
Koji
K
Anada
Masahiro
M
Nambu
Hisanori
H
Shiro
Motoo
M
Hashimoto
Shunichi
S
D001685:Biological Factors / Q000138:chemical synthesis* / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D007659:Ketones / Q000737:chemistry*; D030004:Ligusticum / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
D001685:Biological Factors; D001643:Bridged Bicyclo Compounds; D007659:Ketones; D009942:Organometallic Compounds; D012238:Rhodium