26 / 2023-07-25 14:10:09

Cu-Cumulenylidenes as Intermediates: Allenynylphosphoryls from Cu-Catalyzed Couplings of Diynylic Acetates with H-Phosphoryl Compounds

copper,organophosphorus,allenes,cumulenylidene,non-precious metal catalyst

Phosphorus in Synthetic Chemistry > 1) Phosphorus compounds as catalysts

Cu-Cumulenylidenes as Intermediates: Allenynylphosphoryls from Cu-Catalyzed Couplings of Diynylic Acetates with H-Phosphoryl Compounds

Kaixin Yin,^a Yishuai Fan,^a Li-Biao Han,^b Ruwei Shen*<sup>,a

a</sup>State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211800, China. E-mail: shenrw@njtech.edu.cn

^bZhejiang Yangfan New Materials Company, Ltd., Shangyu, Zhejiang 312369, China

The development of transition metal catalyzed C-P bond formation reactions is  of high importance for organophosphorus synthesis. Based on the site-selective nucleophilic interception of copper-allenylidenes, in 2016 we first report the Cu-catalyzed propargylic substitution of propargyl acetates, propargyl epoxides and penta-1,4-diyn-3-ylacetates with H-phosphoryl compounds to afford phosphoryl allenes, 4-phosphoryl 2,3-allenols and 1-phosphonyl 2,4-diynes in high yields (Scheme 1a).¹ As our continuing interest in the synthetic organophosphorus chemistry,² we disclose here a highly efficient copper-catalyzed coupling reaction of diynylic acetates with H-phosphoryl compounds to provide an expeditious synthesis of a novel class of conjugated allenynylphosphoryls, based on a conception of selective phospha-nucleophilic interception of copper-cumulenylidene intermediates (Scheme 1b).



References:

1. (a) R. Shen, B. Luo, J. Yang, L. Zhang, L. B. Han, Chem. Commun. 2016, 52, 6451. (b) R. Shen, J. Yang, H. Zhao, Y. Feng, L. Zhang, L. B. Han, Chem. Commun. 2016, 52, 11959. (c) R. Shen, J. Yang, B. Luo, L. Zhang, L. B. Han, Adv. Synth. Catal. 2016, 358, 3897. (d) R. Shen, J. Yang, M. Zhang, L. B. Han, Adv. Synth. Catal. 2017, 359, 3626.


2. (a) C. Dong, C. Zhang, X. Wang, R. Shen, Asian J. Org. Chem. 2021, 10, 1514. (b) J. Xiao, Q. Li, R. Shen, S. Shimada, L. B. Han, Adv. Synth. Catal. 2019, 361, 5715. (c) R. Shen, M. Zhang, J. Xiao, C. Dong, L. B. Han, Green Chem. 2018, 20, 5111. (d) M. Zhang, J. Yang, Q. Xu, C. Dong, L. B. Han, R. Shen, Adv. Synth. Catal. 2018, 360, 334. (e) X. Li, Y. Xie, K. Yin, R. Shen, D. Zhu, Synthesis 2022, 54, 2574. (f) X. Wang, C. Zhang, R. Shen, L. B. Han, J. Org. Chem. 2020, 85, 14753.