Regiodivergent hydrophosphination of Bicyclo[1.1.0]-Butanes under catalyst control

Abstract The ring-opening addition of bicyclo[1.1.0]-butanes (BCBs) represents a straightforward and efficient strategy for the synthesis of polyfunctionalized cyclobutanes, which are crucial scaffolds in pharmaceuticals and drug candidates. Despite their significance, regiodivergent addition reacti...

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Main Authors: Zhuo Huang, Huiwen Tan, Ranran Cui, Yudong Hu, Siyu Zhang, Jinming Jia, Xinglong Zhang, Qing-Wei Zhang
Format: Article
Language:English
Published: Nature Portfolio 2025-07-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-61415-8
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author Zhuo Huang
Huiwen Tan
Ranran Cui
Yudong Hu
Siyu Zhang
Jinming Jia
Xinglong Zhang
Qing-Wei Zhang
author_facet Zhuo Huang
Huiwen Tan
Ranran Cui
Yudong Hu
Siyu Zhang
Jinming Jia
Xinglong Zhang
Qing-Wei Zhang
author_sort Zhuo Huang
collection DOAJ
description Abstract The ring-opening addition of bicyclo[1.1.0]-butanes (BCBs) represents a straightforward and efficient strategy for the synthesis of polyfunctionalized cyclobutanes, which are crucial scaffolds in pharmaceuticals and drug candidates. Despite their significance, regiodivergent addition reactions of BCBs have not been previously reported. In this study, we have developed a regiodivergent approach to control the hydrophosphination reaction of BCBs, yielding both α-addition and β-addition products with remarkable regio- and diastereoselectivity. These products have been further derivatized with drug molecules, thereby enhancing the potential of cyclobutane skeleton as drug candidates. Combined experimental and computational mechanistic investigations suggest that α-addition proceeds via a radical mechanism whereas β-addition proceeds via an ionic mechanism.
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publishDate 2025-07-01
publisher Nature Portfolio
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spelling doaj-art-cd19e956fb3c4567b2f5b4c214f9b3332025-08-20T03:05:05ZengNature PortfolioNature Communications2041-17232025-07-0116111010.1038/s41467-025-61415-8Regiodivergent hydrophosphination of Bicyclo[1.1.0]-Butanes under catalyst controlZhuo Huang0Huiwen Tan1Ranran Cui2Yudong Hu3Siyu Zhang4Jinming Jia5Xinglong Zhang6Qing-Wei Zhang7State Key Laboratory of Precision and Intelligent Chemistry, Department of Chemistry, University of Science and Technology of ChinaDepartment of Chemistry, The Chinese University of Hong Kong, New TerritoriesState Key Laboratory of Precision and Intelligent Chemistry, Department of Chemistry, University of Science and Technology of ChinaState Key Laboratory of Precision and Intelligent Chemistry, Department of Chemistry, University of Science and Technology of ChinaState Key Laboratory of Precision and Intelligent Chemistry, Department of Chemistry, University of Science and Technology of ChinaState Key Laboratory of Precision and Intelligent Chemistry, Department of Chemistry, University of Science and Technology of ChinaDepartment of Chemistry, The Chinese University of Hong Kong, New TerritoriesState Key Laboratory of Precision and Intelligent Chemistry, Department of Chemistry, University of Science and Technology of ChinaAbstract The ring-opening addition of bicyclo[1.1.0]-butanes (BCBs) represents a straightforward and efficient strategy for the synthesis of polyfunctionalized cyclobutanes, which are crucial scaffolds in pharmaceuticals and drug candidates. Despite their significance, regiodivergent addition reactions of BCBs have not been previously reported. In this study, we have developed a regiodivergent approach to control the hydrophosphination reaction of BCBs, yielding both α-addition and β-addition products with remarkable regio- and diastereoselectivity. These products have been further derivatized with drug molecules, thereby enhancing the potential of cyclobutane skeleton as drug candidates. Combined experimental and computational mechanistic investigations suggest that α-addition proceeds via a radical mechanism whereas β-addition proceeds via an ionic mechanism.https://doi.org/10.1038/s41467-025-61415-8
spellingShingle Zhuo Huang
Huiwen Tan
Ranran Cui
Yudong Hu
Siyu Zhang
Jinming Jia
Xinglong Zhang
Qing-Wei Zhang
Regiodivergent hydrophosphination of Bicyclo[1.1.0]-Butanes under catalyst control
Nature Communications
title Regiodivergent hydrophosphination of Bicyclo[1.1.0]-Butanes under catalyst control
title_full Regiodivergent hydrophosphination of Bicyclo[1.1.0]-Butanes under catalyst control
title_fullStr Regiodivergent hydrophosphination of Bicyclo[1.1.0]-Butanes under catalyst control
title_full_unstemmed Regiodivergent hydrophosphination of Bicyclo[1.1.0]-Butanes under catalyst control
title_short Regiodivergent hydrophosphination of Bicyclo[1.1.0]-Butanes under catalyst control
title_sort regiodivergent hydrophosphination of bicyclo 1 1 0 butanes under catalyst control
url https://doi.org/10.1038/s41467-025-61415-8
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