Synthesis of bicyclo[4.1.0]heptenes via palladium-catalyzed intramolecular coupling-cyclization of 3-(cyclohexa-2,4-dienyl)pentane-2,4-dione with β-styryl bromides

Ming Chang P Yeh; Wen Cheng Tsao; Yen Jung Wang; Hui Fen Pai

doi:10.1021/om7004386

Synthesis of bicyclo[4.1.0]heptenes via palladium-catalyzed intramolecular coupling-cyclization of 3-(cyclohexa-2,4-dienyl)pentane-2,4-dione with β-styryl bromides

Ming Chang P Yeh, Wen Cheng Tsao, Yen Jung Wang, Hui Fen Pai

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

7 Citations (Scopus)

Abstract

Palladium-catalyzed intramolecular coupling-cyclization of 3-(cyclohexa-2,4-dienyl)pentane-2,4-dione with β-styryl bromides proceeds in regio- and stereoselective fashions to give 2-styryl-substituted bicyclo[4.1.0]hept-3-enes in good yields. The formation of the bicyclo[4.1.0]hept-3-enes was rationalized by starting with oxidative addition of Pd(PPh₃)₄ to the carbon-bromine bond of β-styryl bromide (RBr) to give Pd(R)BrLn. Reaction of Pd(R)BrLn with Ag ₂CO₃ generates a cationic RPd(II)Ln species. Chelation of the RPd(II)Ln cation to both the O-enolate of the ketone and the proximal double bond followed by attack of the enolate on the activated double bond gave a bicyclic η¹-allylpalladium intermediate. The postulated bicyclic η¹-allylpalladium intermediate leads to 2-styryl-substituted bicyclo[4.1.0]hept-3-enes with exclusive regio- and stereoselectivities after reductive elimination.

Original language	English
Pages (from-to)	4271-4277
Number of pages	7
Journal	Organometallics
Volume	26
Issue number	17
DOIs	https://doi.org/10.1021/om7004386
Publication status	Published - 2007 Aug 13

ASJC Scopus subject areas

Inorganic Chemistry
Organic Chemistry

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title = "Synthesis of bicyclo[4.1.0]heptenes via palladium-catalyzed intramolecular coupling-cyclization of 3-(cyclohexa-2,4-dienyl)pentane-2,4-dione with β-styryl bromides",

abstract = "Palladium-catalyzed intramolecular coupling-cyclization of 3-(cyclohexa-2,4-dienyl)pentane-2,4-dione with β-styryl bromides proceeds in regio- and stereoselective fashions to give 2-styryl-substituted bicyclo[4.1.0]hept-3-enes in good yields. The formation of the bicyclo[4.1.0]hept-3-enes was rationalized by starting with oxidative addition of Pd(PPh3)4 to the carbon-bromine bond of β-styryl bromide (RBr) to give Pd(R)BrLn. Reaction of Pd(R)BrLn with Ag 2CO3 generates a cationic RPd(II)Ln species. Chelation of the RPd(II)Ln cation to both the O-enolate of the ketone and the proximal double bond followed by attack of the enolate on the activated double bond gave a bicyclic η1-allylpalladium intermediate. The postulated bicyclic η1-allylpalladium intermediate leads to 2-styryl-substituted bicyclo[4.1.0]hept-3-enes with exclusive regio- and stereoselectivities after reductive elimination.",

author = "Yeh, {Ming Chang P} and Tsao, {Wen Cheng} and Wang, {Yen Jung} and Pai, {Hui Fen}",

year = "2007",

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doi = "10.1021/om7004386",

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AU - Yeh, Ming Chang P

AU - Tsao, Wen Cheng

AU - Wang, Yen Jung

AU - Pai, Hui Fen

PY - 2007/8/13

Y1 - 2007/8/13

N2 - Palladium-catalyzed intramolecular coupling-cyclization of 3-(cyclohexa-2,4-dienyl)pentane-2,4-dione with β-styryl bromides proceeds in regio- and stereoselective fashions to give 2-styryl-substituted bicyclo[4.1.0]hept-3-enes in good yields. The formation of the bicyclo[4.1.0]hept-3-enes was rationalized by starting with oxidative addition of Pd(PPh3)4 to the carbon-bromine bond of β-styryl bromide (RBr) to give Pd(R)BrLn. Reaction of Pd(R)BrLn with Ag 2CO3 generates a cationic RPd(II)Ln species. Chelation of the RPd(II)Ln cation to both the O-enolate of the ketone and the proximal double bond followed by attack of the enolate on the activated double bond gave a bicyclic η1-allylpalladium intermediate. The postulated bicyclic η1-allylpalladium intermediate leads to 2-styryl-substituted bicyclo[4.1.0]hept-3-enes with exclusive regio- and stereoselectivities after reductive elimination.

AB - Palladium-catalyzed intramolecular coupling-cyclization of 3-(cyclohexa-2,4-dienyl)pentane-2,4-dione with β-styryl bromides proceeds in regio- and stereoselective fashions to give 2-styryl-substituted bicyclo[4.1.0]hept-3-enes in good yields. The formation of the bicyclo[4.1.0]hept-3-enes was rationalized by starting with oxidative addition of Pd(PPh3)4 to the carbon-bromine bond of β-styryl bromide (RBr) to give Pd(R)BrLn. Reaction of Pd(R)BrLn with Ag 2CO3 generates a cationic RPd(II)Ln species. Chelation of the RPd(II)Ln cation to both the O-enolate of the ketone and the proximal double bond followed by attack of the enolate on the activated double bond gave a bicyclic η1-allylpalladium intermediate. The postulated bicyclic η1-allylpalladium intermediate leads to 2-styryl-substituted bicyclo[4.1.0]hept-3-enes with exclusive regio- and stereoselectivities after reductive elimination.

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Synthesis of bicyclo[4.1.0]heptenes via palladium-catalyzed intramolecular coupling-cyclization of 3-(cyclohexa-2,4-dienyl)pentane-2,4-dione with β-styryl bromides

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