title: Rh(I)-Catalyzed 1,4-Conjugate Addition of Alkenylboronic Acids to a Cyclopentenone Useful for the Synthesis of Prostaglandins.
abstract: An efficient and trans-diastereoselective Rh(I)-catalyzed 1,4-conjugate addition reaction of alkenylboronic acids and a homochiral (R)-4-silyloxycyclopentenone useful for the synthesis of derivatives of prostaglandins E and F is described for the first time. The reaction functions under mild conditions and is particularly rapid (≤6 h) under low power (50 W) microwave irradiation at 30 °C in MeOH in the presence of a catalytic amount of KOH. Under these conditions, 3 mol % of [RhCl(COD)]2is typically required to produce high yields. The method also functions without microwave irradiation at 3 °C in the presence of a stoichiometric amount of KOH. Under these conditions, only 1.5 mol % of [RhCl(COD)]2is needed, but the reaction is considerably slower. The method accepts a range of aryl- and alkyl-substituted alkenylboronic acids, and its utility has been demonstrated by the synthesis of PGF2α(dinoprost) and tafluprost.
authors.affiliation: Department of Chemistry and Instrumentation Center, National Taiwan Normal University , No. 88, Section 4, Tingzhou Road, Taipei, Taiwan 11677, Republic of China.
authors.forename: Jin-Fong
authors.initials: JF
authors.lastname: Syu
authors.affiliation: Department of Chemistry and Instrumentation Center, National Taiwan Normal University , No. 88, Section 4, Tingzhou Road, Taipei, Taiwan 11677, Republic of China.
authors.forename: Yun-Ting
authors.initials: YT
authors.lastname: Wang
authors.affiliation: ScinoPharm Taiwan, Ltd. No. 1 , Nan-Ke eighth Road, Southern Taiwan Science Park, Shan-Hua, Tainan, Taiwan 74144, Republic of China.
authors.forename: Kung-Cheng
authors.initials: KC
authors.lastname: Liu
authors.affiliation: ScinoPharm Taiwan, Ltd. No. 1 , Nan-Ke eighth Road, Southern Taiwan Science Park, Shan-Hua, Tainan, Taiwan 74144, Republic of China.
authors.forename: Ping-Yu
authors.initials: PY
authors.lastname: Wu
authors.affiliation: ScinoPharm Taiwan, Ltd. No. 1 , Nan-Ke eighth Road, Southern Taiwan Science Park, Shan-Hua, Tainan, Taiwan 74144, Republic of China.
authors.forename: Julian P
authors.initials: JP
authors.lastname: Henschke
authors.affiliation: Department of Chemistry and Instrumentation Center, National Taiwan Normal University , No. 88, Section 4, Tingzhou Road, Taipei, Taiwan 11677, Republic of China.
authors.forename: Hsyueh-Liang
authors.initials: HL
authors.lastname: Wu
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D001897:Boronic Acids / Q000737:chemistry*; D002384:Catalysis; D003517:Cyclopentanes / Q000737:chemistry*; D006878:Hydroxides / Q000737:chemistry; D008872:Microwaves; D017680:Potassium Compounds / Q000737:chemistry; D011453:Prostaglandins / Q000138:chemical synthesis*; D012238:Rhodium / Q000737:chemistry*; D013057:Spectrum Analysis / Q000379:methods
chemical_list: D000475:Alkenes; D001897:Boronic Acids; D003517:Cyclopentanes; D006878:Hydroxides; D017680:Potassium Compounds; D011453:Prostaglandins; D012238:Rhodium; C013905:cyclopentenone; C029943:potassium hydroxide