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多样化的氟代烷烃：光驱动的氟烷基转移乙烯基硼酸酯。

Diversifying fluoroalkanes: light-driven fluoroalkyl transfer vinylboronate esters.

作者信息

Chakrabarti Kaushik, Sunil Chandana, Farris Benjamin M, Berritt Simon, Cassaidy Kyle, Lee Jisun, Szymczak Nathaniel K

机构信息

Department of Chemistry, University of Michigan 930N. University Ann Arbor Michigan 48109 USA

Medicine Design, Pfizer Inc. Eastern Point Rd. Groton CT 06340 USA.

出版信息

Chem Sci. 2025 Mar 24;16(16):6975-6981. doi: 10.1039/d5sc01776a. eCollection 2025 Apr 16.

DOI:10.1039/d5sc01776a
PMID:40134657
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11931429/
Abstract

We outline a new synthetic strategy to prepare tertiary difluoromethylene-containing molecules from fluoroalkane precursors and vinyl-pinacol boronic ester (vinyl-BPin) reagents. Under irradiation, fluoroalkyl(vinyl)pinacol boronate esters [vinyl-BPin-CFR] undergo a conjugate radical addition process to form new C-C bonds, which does not require air-free conditions and tolerates oxygen and nitrogen-containing heterocycles as well as many classical functional groups. We demonstrate the versatility of this method through a one-pot synthetic protocol using RCFH precursors and vinyl-BPin reagents in the presence of a Brønsted base. Widely available fluoroalkanes (HFC-23 and HFC-32) and difluoromethyl heteroarenes are used in this protocol, representing distinct strategies to generate tertiary -CFH, -CF and -CF-heteroarene molecules. Experimental and theoretical mechanistic investigations reveal a reaction sequence involving radical initiation followed by an ionic 1,2-boronate rearrangement.

摘要

我们概述了一种新的合成策略，用于从氟代烷烃前体和乙烯基频哪醇硼酸酯（乙烯基 - BPin）试剂制备含叔二氟亚甲基的分子。在光照下，氟代烷基（乙烯基）频哪醇硼酸酯[乙烯基 - BPin - CFR]会发生共轭自由基加成反应以形成新的C - C键，该反应不需要无氧条件，并且能够耐受含氮和氧的杂环以及许多经典官能团。我们通过在布朗斯特碱存在下使用RCFH前体和乙烯基 - BPin试剂的一锅法合成方案，证明了该方法的通用性。此方案中使用了广泛可得的氟代烷烃（HFC - 23和HFC - 32）和二氟甲基杂芳烃，代表了生成叔 - CFH、 - CF和 - CF - 杂芳烃分子的不同策略。实验和理论机理研究揭示了一个反应序列，该序列涉及自由基引发，随后是离子型1,2 - 硼酸酯重排。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d507/12001898/213fca090fa1/d5sc01776a-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d507/12001898/1b45878cb97e/d5sc01776a-f1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d507/12001898/15145154b3e5/d5sc01776a-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d507/12001898/9410dbf502d7/d5sc01776a-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d507/12001898/4b2f7f5ee54b/d5sc01776a-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d507/12001898/213fca090fa1/d5sc01776a-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d507/12001898/1b45878cb97e/d5sc01776a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d507/12001898/5c0b11980d42/d5sc01776a-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d507/12001898/253e5a06834f/d5sc01776a-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d507/12001898/15145154b3e5/d5sc01776a-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d507/12001898/9410dbf502d7/d5sc01776a-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d507/12001898/4b2f7f5ee54b/d5sc01776a-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d507/12001898/213fca090fa1/d5sc01776a-f7.jpg

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