Rh(I)-Catalyzed 1,4-Conjugate Addition of Alkenylboronic Acids to a Cyclopentenone Useful for the Synthesis of Prostaglandins

Jin Fong Syu, Yun Ting Wang, Kung Cheng Liu, Ping Yu Wu, Julian P. Henschke, Hsyueh-Liang Wu

Research output: Contribution to journalArticle

7 Citations (Scopus)

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)]2 is 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)]2 is 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 PGF (dinoprost) and tafluprost.

Original languageEnglish
Pages (from-to)10832-10844
Number of pages13
JournalJournal of Organic Chemistry
Volume81
Issue number22
DOIs
Publication statusPublished - 2016 Nov 18

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Dinoprost
Microwave irradiation
Microwaves
Prostaglandins
Addition reactions
Acids
Prostaglandins F
Prostaglandins E
Derivatives
cyclopentenone
tafluprost

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Rh(I)-Catalyzed 1,4-Conjugate Addition of Alkenylboronic Acids to a Cyclopentenone Useful for the Synthesis of Prostaglandins. / Syu, Jin Fong; Wang, Yun Ting; Liu, Kung Cheng; Wu, Ping Yu; Henschke, Julian P.; Wu, Hsyueh-Liang.

In: Journal of Organic Chemistry, Vol. 81, No. 22, 18.11.2016, p. 10832-10844.

Research output: Contribution to journalArticle

Syu, Jin Fong ; Wang, Yun Ting ; Liu, Kung Cheng ; Wu, Ping Yu ; Henschke, Julian P. ; Wu, Hsyueh-Liang. / Rh(I)-Catalyzed 1,4-Conjugate Addition of Alkenylboronic Acids to a Cyclopentenone Useful for the Synthesis of Prostaglandins. In: Journal of Organic Chemistry. 2016 ; Vol. 81, No. 22. pp. 10832-10844.
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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)]2 is 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)]2 is 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.",
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AU - Liu, Kung Cheng

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AU - Henschke, Julian P.

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