Journal of the American Chemical Society, volume 140, issue 43, pages 14272-14288
Isonitriles as Stereoelectronic Chameleons: The Donor–Acceptor Dichotomy in Radical Additions
Publication type: Journal Article
Publication date: 2018-10-01
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 15
ISSN: 00027863, 15205126
General Chemistry
Catalysis
Biochemistry
Colloid and Surface Chemistry
Abstract
Radical addition to isonitriles (isocyanides) starts and continues all the way to the transition state (TS) mostly as a simple addition to a polarized π-bond. Only after the TS has been passed, the spin density moves to the α-carbon to form the imidoyl radical, the hallmark intermediate of the 1,1-addition-mediated cascades. Addition of alkyl, aryl, heteroatom-substituted, and heteroatom-centered radicals reveals a number of electronic, supramolecular, and conformational effects potentially useful for the practical control of isonitrile-mediated radical cascade transformations. Addition of alkyl radicals reveals two stereoelectronic preferences. First, the radical attack aligns the incipient C···C bond with the aromatic π-system. Second, one of the C-H/C-C bonds at the radical carbon eclipses the isonitrile N-C bond. Combination of these stereoelectronic preferences with entropic penalty explains why the least exergonic reaction (addition of the t-Bu radical) is also the fastest. Heteroatomic radicals reveal further unusual trends. In particular, the Sn radical addition to the PhNC is much faster than addition of the other group IV radicals, despite forming the weakest bond. This combination of kinetic and thermodynamic properties is ideal for applications in control of radical reactivity via dynamic covalent chemistry and may be responsible for the historically broad utility of Sn radicals ("the tyranny of tin"). In addition to polarity and low steric hindrance, radical attack at the relatively strong π-bond of isonitriles is assisted by "chameleonic" supramolecular interactions of the radical center with both the isonitrile π*-system and lone pair. These interactions are yet another manifestation of supramolecular control of radical chemistry.
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- We do not take into account publications that 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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Gomes G. D. P. et al. Isonitriles as Stereoelectronic Chameleons: The Donor–Acceptor Dichotomy in Radical Additions // Journal of the American Chemical Society. 2018. Vol. 140. No. 43. pp. 14272-14288.
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Gomes G. D. P., Loginova Y., Vatsadze S. Z., Alabugin I. V. Isonitriles as Stereoelectronic Chameleons: The Donor–Acceptor Dichotomy in Radical Additions // Journal of the American Chemical Society. 2018. Vol. 140. No. 43. pp. 14272-14288.
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TY - JOUR
DO - 10.1021/jacs.8b08513
UR - https://doi.org/10.1021%2Fjacs.8b08513
TI - Isonitriles as Stereoelectronic Chameleons: The Donor–Acceptor Dichotomy in Radical Additions
T2 - Journal of the American Chemical Society
AU - Loginova, Yulia
AU - Gomes, Gabriel Dos Passos
AU - Vatsadze, Sergey Z.
AU - Alabugin, Igor V.
PY - 2018
DA - 2018/10/01 00:00:00
PB - American Chemical Society (ACS)
SP - 14272-14288
IS - 43
VL - 140
SN - 0002-7863
SN - 1520-5126
ER -
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@article{2018_Gomes,
author = {Yulia Loginova and Gabriel Dos Passos Gomes and Sergey Z. Vatsadze and Igor V. Alabugin},
title = {Isonitriles as Stereoelectronic Chameleons: The Donor–Acceptor Dichotomy in Radical Additions},
journal = {Journal of the American Chemical Society},
year = {2018},
volume = {140},
publisher = {American Chemical Society (ACS)},
month = {oct},
url = {https://doi.org/10.1021%2Fjacs.8b08513},
number = {43},
pages = {14272--14288},
doi = {10.1021/jacs.8b08513}
}
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MLA
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Gomes, Gabriel Dos Passos, et al. “Isonitriles as Stereoelectronic Chameleons: The Donor–Acceptor Dichotomy in Radical Additions.” Journal of the American Chemical Society, vol. 140, no. 43, Oct. 2018, pp. 14272-14288. https://doi.org/10.1021%2Fjacs.8b08513.