Unexpected Insertion of CO2 into the Pentacoordinate P鈥揘 Bond: Atherton鈥揟odd-Type Reaction of Hydrospirophosphorane with Amines

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• 作者：Shuxia Cao ; Peng Gao ; Yanchun Guo ; Huamin Zhao ; Jun Wang ; Yifan Liu ; Yufen Zhao
• 刊名：Journal of Organic Chemistry
• 出版年：2013
• 出版时间：November 15, 2013
• 年：2013
• 卷：78
• 期：22
• 页码：11283-11293
• 全文大小：467K
• 年卷期：v.78,no.22(November 15, 2013)
• ISSN：1520-6904

文摘

The Atherton鈥揟odd-type reaction of pentacoordinate hydrospirophosphoranes with amines was investigated, and a novel CO₂ insertion reaction into the pentacoordinate P鈥揘 bond under mild conditions was developed. The mechanism and stereochemistry of the CO₂ insertion reaction between hydrospirophosphoranes and secondary amines were proposed via a carbon-13 labeling experiment, a ³¹P NMR tracing experiment, and X-ray diffraction analysis. The chlorinated spirophosphorane intermediate was first generated with stereoretention of the configuration at phosphorus and subsequently was attacked by a carbamate anion formed from CO₂ and a secondary amine. It was found that rear attack of nucleophilic substitution with stereoinversion at pentacoordinate phosphorus was the preferred route, although front attack happened for sterically hindered reactants. The configuration of the CO₂ insertion product depended mainly upon the original phosphorus configuration of the hydrospirophosphoranes.