Merging Photoredox with 1,2-Metallate Rearrangements: The Photochemical Alkylation of Vinyl Boronate Complexes

Mattia Silvi; Christopher Sandford; Varinder K. Aggarwal

doi:10.1021/jacs.7b02569

Merging Photoredox with 1,2-Metallate Rearrangements: The Photochemical Alkylation of Vinyl Boronate Complexes

Mattia Silvi, Christopher Sandford, Varinder K. Aggarwal^*

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

164 Citations (Scopus)

410 Downloads (Pure)

Abstract

Vinyl boronates react with electron-deficient alkyl iodides in the presence of visible light to give boronic esters in which two new C-C bonds have been created. The reaction occurs by radical addition of an electron-deficient alkyl radical to the vinyl boronate followed by electron transfer with another molecule of alkyl iodide, continuing the chain, and triggering a 1,2-metalate rearrangement. In a number of cases, the use of a photoredox catalyst enhances yields significantly. The scope of the radical precursor includes α-iodo ketones, esters, nitriles, primary amides, α-fluorinated halo-acetates and perfluoroalkyl iodides.

Original language	English
Pages (from-to)	5736-5739
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	139
Issue number	16
DOIs	https://doi.org/10.1021/jacs.7b02569
Publication status	Published - 12 Apr 2017

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Organic & Biological

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10.1021/jacs.7b02569

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PHOTO-BORAD: Fellowship - Mattia Silvi
Aggarwal, V. K. (Principal Investigator)
1/03/17 → 28/02/19
Project: Research
3-month Core Capability for Chemistry Research
Crosby, J. (Principal Investigator)
1/01/13 → 1/04/13
Project: Research

Professor Varinder K Aggarwal
- V.Aggarwalbristol.acuk
- School of Chemistry - Alfred Capper Pass Chair of Chemistry
Person: Academic

Cite this

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title = "Merging Photoredox with 1,2-Metallate Rearrangements: The Photochemical Alkylation of Vinyl Boronate Complexes",

abstract = "Vinyl boronates react with electron-deficient alkyl iodides in the presence of visible light to give boronic esters in which two new C-C bonds have been created. The reaction occurs by radical addition of an electron-deficient alkyl radical to the vinyl boronate followed by electron transfer with another molecule of alkyl iodide, continuing the chain, and triggering a 1,2-metalate rearrangement. In a number of cases, the use of a photoredox catalyst enhances yields significantly. The scope of the radical precursor includes α-iodo ketones, esters, nitriles, primary amides, α-fluorinated halo-acetates and perfluoroalkyl iodides.",

author = "Mattia Silvi and Christopher Sandford and Aggarwal, \{Varinder K.\}",

year = "2017",

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doi = "10.1021/jacs.7b02569",

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T2 - The Photochemical Alkylation of Vinyl Boronate Complexes

AU - Silvi, Mattia

AU - Sandford, Christopher

AU - Aggarwal, Varinder K.

PY - 2017/4/12

Y1 - 2017/4/12

N2 - Vinyl boronates react with electron-deficient alkyl iodides in the presence of visible light to give boronic esters in which two new C-C bonds have been created. The reaction occurs by radical addition of an electron-deficient alkyl radical to the vinyl boronate followed by electron transfer with another molecule of alkyl iodide, continuing the chain, and triggering a 1,2-metalate rearrangement. In a number of cases, the use of a photoredox catalyst enhances yields significantly. The scope of the radical precursor includes α-iodo ketones, esters, nitriles, primary amides, α-fluorinated halo-acetates and perfluoroalkyl iodides.

AB - Vinyl boronates react with electron-deficient alkyl iodides in the presence of visible light to give boronic esters in which two new C-C bonds have been created. The reaction occurs by radical addition of an electron-deficient alkyl radical to the vinyl boronate followed by electron transfer with another molecule of alkyl iodide, continuing the chain, and triggering a 1,2-metalate rearrangement. In a number of cases, the use of a photoredox catalyst enhances yields significantly. The scope of the radical precursor includes α-iodo ketones, esters, nitriles, primary amides, α-fluorinated halo-acetates and perfluoroalkyl iodides.

U2 - 10.1021/jacs.7b02569

DO - 10.1021/jacs.7b02569

M3 - Article (Academic Journal)

C2 - 28402109

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SN - 0002-7863

VL - 139

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 16

ER -

Merging Photoredox with 1,2-Metallate Rearrangements: The Photochemical Alkylation of Vinyl Boronate Complexes

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Projects

PHOTO-BORAD: Fellowship - Mattia Silvi

3-month Core Capability for Chemistry Research

Profiles

Professor Varinder K Aggarwal

Cite this