Synthesis of a core carbon framework of cyanosporasides A and B.
Treatment of 3-(2-ethynylphenyl)prop-2-ynyl benzenesulfinate with 2.5 mol % of [RhCl(CO)(2)](2) at 40 degrees C under an atmosphere of CO effected the successive 2,3-sigmatropic rearrangement and carbonylative [2 + 2 + 1] ring-closing reaction to afford the 8-(phenylsulfonyl)-1H-cyclopent[a]-inden-2-one in a high yield. Chemical modification of the ring-closed product via lipase-mediated optical resolution produced the optically active 3-acetoxy-3a-cyclohexyloxy-3,3a-dihydrocyclopent-[a]indene skeleton, the core carbon framework of cyanosporasides A and B.
Aburano
Daisuke
D
Division of Pharmaceutical Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
Inagaki
Fuyuhiko
F
Tomonaga
Shoichirou
S
Mukai
Chisato
C
D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D006027:Glycosides / Q000138:chemical synthesis* / Q000737:chemistry; D007192:Indenes / Q000138:chemical synthesis* / Q000737:chemistry; D008049:Lipase / Q000737:chemistry / Q000378:metabolism; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D011551:Pseudomonas fluorescens / Q000201:enzymology; D012238:Rhodium / Q000737:chemistry; D013237:Stereoisomerism
D006027:Glycosides; D007192:Indenes; D009942:Organometallic Compounds; C514853:cyanosporaside A; C514854:cyanosporaside B; D002244:Carbon; D012238:Rhodium; D008049:Lipase