Combined Furan C–H Activation and Furyl Ring-Opening by an Iron(II) Complex

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• 作者：Kathleen H. Taylor ; Steven E. Kalman ; T. Brent Gunnoe ; Michal Sabat
• 刊名：Organometallics
• 出版年：2016
• 出版时间：June 13, 2016
• 年：2016
• 卷：35
• 期：11
• 页码：1978-1985
• 全文大小：479K
• 年卷期：0
• ISSN：1520-6041

文摘

Cp*Fe[P(OCH₂)₃CEt]₂Ph (Cp* = η⁵-1,2,3,4,5-pentamethylcyclopentadienyl, P(OCH₂)₃CEt = 2,6,7-trioxa-1-phosphabicyclo[2,2,1]heptane) reacts with furan and 2-methylfuran under photolytic conditions to selectively activate the α-C–H bond to produce Cp*Fe[P(OCH₂)₃CEt]₂(2-furyl) and Cp*Fe[P(OCH₂)₃CEt]₂[2-(5-methylfuryl)], respectively. Cp*Fe[P(OCH₂)₃CEt]₂(2-furyl) reacts with internal alkynes (2-butyne, 3-hexyne, 1-phenyl-1-propyne) under photolytic conditions to produce sandwich complexes of the type Cp*Fe[η⁵-C₅R₄(CH═CHCHO)] (R = alkyl and/or aryl). Experimental data suggest a mechanism that involves phosphite dissociation and successive alkyne insertions into the Fe–furyl bond followed by furyl ring opening. Similarly, the methylfuryl analogue Cp*Fe[P(OCH₂)₃CEt]₂[2-(5-methylfuryl)] reacts with 2-butyne to produce Cp*Fe[η⁵-C₅Me₄(CH═CHCOCH₃)].