Open Access
Science, volume 349, issue 6255, pages 1532-1536
O–H hydrogen bonding promotes H-atom transfer from α C–H bonds for C-alkylation of alcohols
Publication type: Journal Article
Publication date: 2015-09-25
PubMed ID:
26316601
Multidisciplinary
Abstract
A trio helps activate C-H bonds in alcohols Enzymes can accelerate chemical reactions by activating specific portions of a molecule through well-placed H bonds. Jeffrey et al. showcase the power of H-bonding in a synthetic context. Here, reactivity at the C centers of alcohols is selectively induced by using an H-bonding catalyst to bind the hydroxyl group of the alcohol. The adjacent C-H bonds now become susceptible to a reaction accelerated by another pair of catalysts. In combination, the trio of catalysts promotes C-C bond formation at the alcohol C within an array of competing sites. Science, this issue p. 1532 Hydrogen bonding confers site selectivity in a carbon-carbon bond-forming reaction between alcohols and olefins. The efficiency and selectivity of hydrogen atom transfer from organic molecules are often difficult to control in the presence of multiple potential hydrogen atom donors and acceptors. Here, we describe the mechanistic evaluation of a mode of catalytic activation that accomplishes the highly selective photoredox α-alkylation/lactonization of alcohols with methyl acrylate via a hydrogen atom transfer mechanism. Our studies indicate a particular role of tetra-n-butylammonium phosphate in enhancing the selectivity for α C–H bonds in alcohols in the presence of allylic, benzylic, α-C=O, and α-ether C–H bonds.
Top-30
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American Chemical Society (ACS)
153 publications, 35.66%
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1 publication, 0.23%
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1 publication, 0.23%
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The Chemical Society of Japan
1 publication, 0.23%
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1 publication, 0.23%
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- We do not take into account publications without a DOI.
- Statistics recalculated only for publications connected to researchers, organizations and labs registered on the platform.
- Statistics recalculated weekly.
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Jeffrey J. L., Terrett J. A., Macmillan D. W. C. O–H hydrogen bonding promotes H-atom transfer from α C–H bonds for C-alkylation of alcohols // Science. 2015. Vol. 349. No. 6255. pp. 1532-1536.
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Jeffrey J. L., Terrett J. A., Macmillan D. W. C. O–H hydrogen bonding promotes H-atom transfer from α C–H bonds for C-alkylation of alcohols // Science. 2015. Vol. 349. No. 6255. pp. 1532-1536.
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TY - JOUR
DO - 10.1126/science.aac8555
UR - https://doi.org/10.1126/science.aac8555
TI - O–H hydrogen bonding promotes H-atom transfer from α C–H bonds for C-alkylation of alcohols
T2 - Science
AU - Jeffrey, Jenna L
AU - Terrett, Jack A
AU - Macmillan, David W C
PY - 2015
DA - 2015/09/25 00:00:00
PB - American Association for the Advancement of Science (AAAS)
SP - 1532-1536
IS - 6255
VL - 349
PMID - 26316601
SN - 0036-8075
SN - 1095-9203
ER -
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@article{2015_Jeffrey,
author = {Jenna L Jeffrey and Jack A Terrett and David W C Macmillan},
title = {O–H hydrogen bonding promotes H-atom transfer from α C–H bonds for C-alkylation of alcohols},
journal = {Science},
year = {2015},
volume = {349},
publisher = {American Association for the Advancement of Science (AAAS)},
month = {sep},
url = {https://doi.org/10.1126/science.aac8555},
number = {6255},
pages = {1532--1536},
doi = {10.1126/science.aac8555}
}
Cite this
MLA
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Jeffrey, Jenna L., et al. “O–H hydrogen bonding promotes H-atom transfer from α C–H bonds for C-alkylation of alcohols.” Science, vol. 349, no. 6255, Sep. 2015, pp. 1532-1536. https://doi.org/10.1126/science.aac8555.