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CC BY-ND-NC 4.0 · SynOpen 2017; 01(01): 0068-0075
DOI: 10.1055/s-0036-1590969
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Diastereoselective [Cu(MeCN)4BF4/BF3·Et2O]-Catalyzed Cyclopropenation of Alkynes: Asymmetric Synthesis of β-Amino-α-cyclopropenyl Phosphonates

Haihong Ge
a   State Key Laboratory of Elemento-Organic Chemistry, Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, P. R. of China   Email: miaozhiwei@nankai.edu.cn
,
Shuang Liu
a   State Key Laboratory of Elemento-Organic Chemistry, Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, P. R. of China   Email: miaozhiwei@nankai.edu.cn
,
Yan Cai
a   State Key Laboratory of Elemento-Organic Chemistry, Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, P. R. of China   Email: miaozhiwei@nankai.edu.cn
,
Zenghui Gao
a   State Key Laboratory of Elemento-Organic Chemistry, Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, P. R. of China   Email: miaozhiwei@nankai.edu.cn
,
Siyi Du
a   State Key Laboratory of Elemento-Organic Chemistry, Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, P. R. of China   Email: miaozhiwei@nankai.edu.cn
,
Zhiwei Miao  *
a   State Key Laboratory of Elemento-Organic Chemistry, Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, P. R. of China   Email: miaozhiwei@nankai.edu.cn
b   Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300071, P. R. of China
,
Guixian Xie*
c   College of Resources and Environment, Hunan Agricultural University, Changsha 410128, P. R. of China   Email: xieguixian@126.com
› Author AffiliationsWe thank the Committee of Science and Technology of Tianjin (15JCYBJC20700), the Tianjin Rural Work Committee (201604020) and State Key Laboratory of Elemento-Organic Chemistry in Nankai University for financial support.
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Publication History

Received: 31 May 2017

Accepted after revision: 06 July 2017

Publication Date:
03 August 2017 (online)

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Abstract

The diastereospecific formation of β-amino-α-cyclopropenyl phosphonates has been achieved in moderate yields from the cyclopropenation of 1-alkynes with dialkyl α-diazophosphonates. The reaction was performed by using a combined catalyst consisting of Cu(MeCN)4BF4 and BF3·Et2O as additive in dichloromethane at 40 °C. A possible mechanism for the reaction has been proposed to explain the origin of the activation and the asymmetric induction. This method provides a versatile approach to β-amino-α-cyclopropenylphosphonates containing a quaternary stereogenic center with good efficiency and diastereoselectivity.

Key words

cyclopropenation - α-diazophosphonates - asymmetric synthesis - cyclopropenylphosphonates - Cu(MeCN)4BF4/BF3·Et2O

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590969.
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