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氧连接的生发受阻路易斯对的合成及其在小分子活化中的应用。

Synthesis of an oxygen-linked germinal frustrated Lewis pair and its application in small molecule activation.

作者信息

Wang Yiheng, Li Zhen Hua, Wang Huadong

机构信息

Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University Songhu Road 2005 Shanghai 200438 China.

State Key Laboratory of Elemento-Organic Chemistry, Nankai University Tianjin 300071 China

出版信息

RSC Adv. 2018 Jul 23;8(46):26271-26276. doi: 10.1039/c8ra05108a. eCollection 2018 Jul 19.

DOI:10.1039/c8ra05108a
PMID:35541977
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9082762/
Abstract

Reaction of MesP(O)Li with (CF)BCl gave access to an oxygen-linked germinal intramolecular frustrated Lewis pair MesP(O)B(CF) (1). Compound 1 is stable at room temperature and only decomposes when heated to 90 °C. NMR analysis and theoretical analysis revealed the frustrated nature between the boron and phosphorus centers. Compound 1 shows typical frustrated Lewis pair reactivity when treated with dihydrogen, carbon dioxide, alkyne and alkene. The reaction of 1 with isoprene resulted in selective formation of 3,4-phosphoryl/boryl addition product 8.

摘要

MesP(O)Li与(CF)BCl反应得到了一个氧连接的分子内邻位受阻路易斯酸碱对MesP(O)B(CF)（1）。化合物1在室温下稳定，仅在加热至90℃时分解。核磁共振分析和理论分析揭示了硼和磷中心之间的受阻性质。化合物1在与氢气、二氧化碳、炔烃和烯烃反应时表现出典型的受阻路易斯酸碱对反应活性。1与异戊二烯反应选择性地生成了3,4-磷酰基/硼基加成产物8。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/19113a2a320a/c8ra05108a-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/d9acb21b26f2/c8ra05108a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/17ce305d2999/c8ra05108a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/3c195f37797c/c8ra05108a-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/2ba382a7702e/c8ra05108a-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/b1c8462eb5f6/c8ra05108a-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/1df67e9d4f8b/c8ra05108a-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/13de18fcedf6/c8ra05108a-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/3cbcf5ae73a4/c8ra05108a-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/19113a2a320a/c8ra05108a-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/d9acb21b26f2/c8ra05108a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/17ce305d2999/c8ra05108a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/3c195f37797c/c8ra05108a-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/2ba382a7702e/c8ra05108a-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/b1c8462eb5f6/c8ra05108a-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/1df67e9d4f8b/c8ra05108a-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/13de18fcedf6/c8ra05108a-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/3cbcf5ae73a4/c8ra05108a-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c42/9082762/19113a2a320a/c8ra05108a-s5.jpg

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