Carbonylation of 1-Lithiobutadiene with Carbon Monoxide Followed by Intramolecular Acyllithiation of C鈺怌 Double Bond and Intermolecular Acylation with Acid Chloride: Scope, Applications, and Mechanist

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• 作者：Heng Li ; Lantao Liu ; Fei Zhao ; Congyang Wang ; Chao Wang ; Qiuling Song ; Wen-Xiong Zhang ; Zhenfeng Xi
• 刊名：The Journal of Organic Chemistry
• 出版年：2012
• 出版时间：May 18, 2012
• 年：2012
• 卷：77
• 期：10
• 页码：4793-4800
• 全文大小：447K
• 年卷期：v.77,no.10(May 18, 2012)
• ISSN：1520-6904

文摘

The carbonylation of a 1-lithio-1,3-butadiene derivative with CO gave rise to a butadienyl acyllithio intermediate, which underwent an immediate intramolecular acyllithiation of the C鈺?/b>C double bond, affording a lithio cyclopentadienyl enolate. The X-ray structural analysis of the enolate revealed a dimer connected with a 鈥淟i₂O₂鈥?four-membered ring. Subsequent intermolecular acylation of this enolate with acid chlorides afforded 尾-keto-3-cyclopentenones, 纬-keto-2-cyclopentenones, or cyclopentadienyl ester derivatives. The stereo- and regioselectivity of the in situ generated lithio cyclopentadienyl enolate with various acid chlorides was investigated and analyzed, showing that the formation of the above products was significantly dependent on both the substituents on the butadienyl skeleton and the bulkiness of acid chlorides.