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Isonitriles as Stereoelectronic Chameleons: The Donor–Acceptor Dichotomy in Radical Additions by Gabriel dos Passos Gomes; Yulia Loginova; Sergey Z. Vatsadze; Igor V. Alabugin is a Chemistry article available to read on EtoBox.

What is Isonitriles as Stereoelectronic Chameleons: The Donor–Acceptor Dichotomy in Radical Additions about?

Radical addition to isonitriles (isocyanides) starts and continues all the way to the 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 kineti

Who reads Isonitriles as Stereoelectronic Chameleons: The Donor–Acceptor Dichotomy in Radical Additions?

Author

Gabriel dos Passos Gomes; Yulia Loginova; Sergey Z. Vatsadze; Igor V. Alabugin

Published

2018

Language

EN

Field

Chemistry (Physical Sciences)