Facile synthesis of carbotetracycles via gold(i)-catalyzed cyclization of unactivated cyclic 1-aryl-6,8-dien-1-ynes

Ming Chang P. Yeh, Wen Cheng Tsao, Bo Jen Lee, Tzu G. Lin

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

The gold(I)-catalyzed cyclization of the cyclohexa-1,3-diene bearing a terminal alkyne and a gemdiester in the tether proceeds via a cationic gold intermediate to give a tetrahydromethyleneindene derivative. Changing the gem-diester to a gem-diketone in the tether, the transient gold-stabilized carbocation is trapped intramolecularly by a methyl ketone to afford a tricyclo[5.4.04,8]undecane ring skeleton. Under the same reaction conditions, aryl-substituted cyclohexadienynes afford hexahydroacephenanthrylene rings in a diastereoselective fashion and in good yields. The reaction proceeded via attack of the aryl group onto the gold-stabilized carbocations followed by aromatization and protodemetalation to generate the tetracarbocycles. This cycloaddition can be applied to the synthesis of pentahydronapthoazulenes from aryl-substituted cycloheptadienynes and the gold(I) catalyst.

Original languageEnglish
Pages (from-to)5326-5332
Number of pages7
JournalOrganometallics
Volume27
Issue number20
DOIs
Publication statusPublished - 2008 Oct 27

Fingerprint

Cyclization
Gold
gold
Gems
synthesis
Bearings (structural)
Aromatization
Alkynes
Cycloaddition
rings
cycloaddition
dienes
alkynes
Ketones
musculoskeletal system
ketones
attack
Derivatives
catalysts
Catalysts

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Facile synthesis of carbotetracycles via gold(i)-catalyzed cyclization of unactivated cyclic 1-aryl-6,8-dien-1-ynes. / Yeh, Ming Chang P.; Tsao, Wen Cheng; Lee, Bo Jen; Lin, Tzu G.

In: Organometallics, Vol. 27, No. 20, 27.10.2008, p. 5326-5332.

Research output: Contribution to journalArticle

@article{dc89a3e43f3c4bdaa455efeaab7cf868,
title = "Facile synthesis of carbotetracycles via gold(i)-catalyzed cyclization of unactivated cyclic 1-aryl-6,8-dien-1-ynes",
abstract = "The gold(I)-catalyzed cyclization of the cyclohexa-1,3-diene bearing a terminal alkyne and a gemdiester in the tether proceeds via a cationic gold intermediate to give a tetrahydromethyleneindene derivative. Changing the gem-diester to a gem-diketone in the tether, the transient gold-stabilized carbocation is trapped intramolecularly by a methyl ketone to afford a tricyclo[5.4.04,8]undecane ring skeleton. Under the same reaction conditions, aryl-substituted cyclohexadienynes afford hexahydroacephenanthrylene rings in a diastereoselective fashion and in good yields. The reaction proceeded via attack of the aryl group onto the gold-stabilized carbocations followed by aromatization and protodemetalation to generate the tetracarbocycles. This cycloaddition can be applied to the synthesis of pentahydronapthoazulenes from aryl-substituted cycloheptadienynes and the gold(I) catalyst.",
author = "Yeh, {Ming Chang P.} and Tsao, {Wen Cheng} and Lee, {Bo Jen} and Lin, {Tzu G.}",
year = "2008",
month = "10",
day = "27",
doi = "10.1021/om8005917",
language = "English",
volume = "27",
pages = "5326--5332",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "20",

}

TY - JOUR

T1 - Facile synthesis of carbotetracycles via gold(i)-catalyzed cyclization of unactivated cyclic 1-aryl-6,8-dien-1-ynes

AU - Yeh, Ming Chang P.

AU - Tsao, Wen Cheng

AU - Lee, Bo Jen

AU - Lin, Tzu G.

PY - 2008/10/27

Y1 - 2008/10/27

N2 - The gold(I)-catalyzed cyclization of the cyclohexa-1,3-diene bearing a terminal alkyne and a gemdiester in the tether proceeds via a cationic gold intermediate to give a tetrahydromethyleneindene derivative. Changing the gem-diester to a gem-diketone in the tether, the transient gold-stabilized carbocation is trapped intramolecularly by a methyl ketone to afford a tricyclo[5.4.04,8]undecane ring skeleton. Under the same reaction conditions, aryl-substituted cyclohexadienynes afford hexahydroacephenanthrylene rings in a diastereoselective fashion and in good yields. The reaction proceeded via attack of the aryl group onto the gold-stabilized carbocations followed by aromatization and protodemetalation to generate the tetracarbocycles. This cycloaddition can be applied to the synthesis of pentahydronapthoazulenes from aryl-substituted cycloheptadienynes and the gold(I) catalyst.

AB - The gold(I)-catalyzed cyclization of the cyclohexa-1,3-diene bearing a terminal alkyne and a gemdiester in the tether proceeds via a cationic gold intermediate to give a tetrahydromethyleneindene derivative. Changing the gem-diester to a gem-diketone in the tether, the transient gold-stabilized carbocation is trapped intramolecularly by a methyl ketone to afford a tricyclo[5.4.04,8]undecane ring skeleton. Under the same reaction conditions, aryl-substituted cyclohexadienynes afford hexahydroacephenanthrylene rings in a diastereoselective fashion and in good yields. The reaction proceeded via attack of the aryl group onto the gold-stabilized carbocations followed by aromatization and protodemetalation to generate the tetracarbocycles. This cycloaddition can be applied to the synthesis of pentahydronapthoazulenes from aryl-substituted cycloheptadienynes and the gold(I) catalyst.

UR - http://www.scopus.com/inward/record.url?scp=55249110856&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=55249110856&partnerID=8YFLogxK

U2 - 10.1021/om8005917

DO - 10.1021/om8005917

M3 - Article

AN - SCOPUS:55249110856

VL - 27

SP - 5326

EP - 5332

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 20

ER -