Iron-Catalyzed Borylation of Ketones to α-Hydroxyboronates

doi:10.6023/cjoc202010022

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (2): 661-668.DOI: 10.6023/cjoc202010022 Previous Articles Next Articles

Special Issue: 热点论文虚拟合集

Article

铁催化酮羰基的硼化反应合成α-羟基硼酸酯

朱庆^a^,^b, 夏春谷^a, 刘超^a^,^*()

a 中国科学院兰州化学物理研究所兰州 730000
b 中国科学院大学北京 100049

收稿日期:2020-10-16 修回日期:2020-10-30 发布日期:2020-11-04
通讯作者: 刘超
作者简介:
* Corresponding author. E-mail: chaoliu@licp.cas.cn
基金资助:
国家自然科学基金(21673261); 国家自然科学基金(91745110); 国家自然科学基金(21872156); 江苏省自然科学基金(BK20190002); 江苏省自然科学基金(BK20181194); 中国科学院青年创新促进会(2018458)

Iron-Catalyzed Borylation of Ketones to α-Hydroxyboronates

Qing Zhu^a^,^b, Chungu Xia^a, Chao Liu^a^,^*()

a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000
b University of Chinese Academy of Sciences, Beijing 100049

Received:2020-10-16 Revised:2020-10-30 Published:2020-11-04
Contact: Chao Liu
Supported by:
the National Natural Science Foundation of China(21673261); the National Natural Science Foundation of China(91745110); the National Natural Science Foundation of China(21872156); the Natural Science Foundation of Jiangsu Province(BK20190002); the Natural Science Foundation of Jiangsu Province(BK20181194); and the Youth Innovation Promotion Association CAS(2018458)

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Abstract

Fe-catalyzed borylation of ketones to access tertiary α-hydroxyboronates has been demonstrated. In this transformation, commercially available FeBr₂ was used as the catalyst, alcohols have been added to accelerate the transformation and avoid the side reaction. Various aliphatic ketones with different functional groups have been converted into tertiary α-hydroxyboronates. This transformation showed a particular tolerance for ketones with steric hinderance, which was distinguished from the traditional Cu catalyst. A gram scale reaction was also available. The alcoholic C—O functionalizations based onα-hydroxyboronates have been realized to access tertiary alkyl boronic esters, gem-diborylalkanes and gem- silylborylalkanes.

Key words: iron catalyst, α-hydroxyboronates, borylation, ketones

Cite this article

Qing Zhu, Chungu Xia, Chao Liu. Iron-Catalyzed Borylation of Ketones to α-Hydroxyboronates[J]. Chinese Journal of Organic Chemistry, 2021, 41(2): 661-668.

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Fig. & Tab. 5

Scheme 1. Cu-catalyzed borylation of aldehydes and ketones

Scheme 2. Our work in iron-catalyzed borylation of carbonyl compounds

Table 1. Reaction parameters of the borylation of ketonesa

Table 2. Scope of substrates

Scheme 4. Alcoholic C—O functionalizations based on α-hy- droxy boronates

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铁催化酮羰基的硼化反应合成α-羟基硼酸酯

Iron-Catalyzed Borylation of Ketones to α-Hydroxyboronates

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Fig. & Tab. 5

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