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Nature Communications, volume 12, issue 1, publication number 2131

Tuning the reactivity of alkoxyl radicals from 1,5-hydrogen atom transfer to 1,2-silyl transfer

Zhaoliang Yang ¹

Yunhong Niu ¹

Xiaoqian He ²

Suo Chen ¹

Shanshan Liu ¹

Zhengyu Li ¹

Xiang Chen ¹

Yunxiao Zhang ¹

Yu Lan ^{2, 3}

Xiao Shen ¹

Hide authors affiliations Show authors affiliations: 3 affiliations

The Institute for Advanced Studies, Engineering Research Center of Organosilicon Compounds and Materials, Ministry of Education, Wuhan University, Wuhan, People’s Republic of China |

School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing, People’s Republic of China |

College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, People’s Republic of China |

Publication type: Journal Article

Publication date: 2021-04-09

Springer Nature

Journal: Nature Communications

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Impact factor: 16.6

ISSN: 20411723, 20411723

DOI: 10.1038/s41467-021-22382-y

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General Chemistry

General Biochemistry, Genetics and Molecular Biology

General Physics and Astronomy

Abstract

Controlling the reactivity of reactive intermediates is essential to achieve selective transformations. Due to the facile 1,5-hydrogen atom transfer (HAT), alkoxyl radicals have been proven to be important synthetic intermediates for the δ-functionalization of alcohols. Herein, we disclose a strategy to inhibit 1,5-HAT by introducing a silyl group into the α-position of alkoxyl radicals. The efficient radical 1,2-silyl transfer (SiT) allows us to make various α-functionalized products from alcohol substrates. Compared with the direct generation of α-carbon radicals from oxidation of α-C-H bond of alcohols, the 1,2-SiT strategy distinguishes itself by the generation of alkoxyl radicals, the tolerance of many functional groups, such as intramolecular hydroxyl groups and C-H bonds next to oxygen atoms, and the use of silyl alcohols as limiting reagents. The generation of α-carbon radicals from alkoxyl radicals is challenging because 1,2-hydrogen atom transfer (HAT) is usually less favoured than 1,5-HAT. Here, the authors report a strategy to inhibit 1,5-HAT by introducing a silyl group into the α-position of alkoxyl radicals, enabling preparation of α-alkoxylimino alcohols and α-heteroaryl alcohols.

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Yang Z. et al. Tuning the reactivity of alkoxyl radicals from 1,5-hydrogen atom transfer to 1,2-silyl transfer // Nature Communications. 2021. Vol. 12. No. 1. 2131

GOST all authors (up to 50) Copy

Yang Z., Niu Y., He X., Chen S., Liu S., Li Z., Chen X., Zhang Y., Lan Yu., Shen X. Tuning the reactivity of alkoxyl radicals from 1,5-hydrogen atom transfer to 1,2-silyl transfer // Nature Communications. 2021. Vol. 12. No. 1. 2131

RIS |

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TY - JOUR

DO - 10.1038/s41467-021-22382-y

UR - https://doi.org/10.1038/s41467-021-22382-y

TI - Tuning the reactivity of alkoxyl radicals from 1,5-hydrogen atom transfer to 1,2-silyl transfer

T2 - Nature Communications

AU - Yang, Zhaoliang

AU - Niu, Yunhong

AU - He, Xiaoqian

AU - Chen, Suo

AU - Liu, Shanshan

AU - Li, Zhengyu

AU - Chen, Xiang

AU - Zhang, Yunxiao

AU - Lan, Yu

AU - Shen, Xiao

PY - 2021

DA - 2021/04/09 00:00:00

PB - Springer Nature

IS - 1

VL - 12

SN - 2041-1723

ER -

BibTex

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BibTex Copy

@article{2021_Yang,

author = {Zhaoliang Yang and Yunhong Niu and Xiaoqian He and Suo Chen and Shanshan Liu and Zhengyu Li and Xiang Chen and Yunxiao Zhang and Yu Lan and Xiao Shen},

title = {Tuning the reactivity of alkoxyl radicals from 1,5-hydrogen atom transfer to 1,2-silyl transfer},

journal = {Nature Communications},

year = {2021},

volume = {12},

publisher = {Springer Nature},

month = {apr},

url = {https://doi.org/10.1038/s41467-021-22382-y},

number = {1},

doi = {10.1038/s41467-021-22382-y}

}

Found error?

Publisher

Springer Nature

Journal

Nature Communications

Quartile SCImago

Quartile WOS

Impact factor

16.6

ISSN

20411723 (Print)
20411723 (Electronic)