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Activation of Low-Valent Titanium Reagents with Iodine:  Facile Low-Temperature McMurry Reaction and N/O-Debenzylation/Deallylation

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    Activation of Low-Valent Titanium Reagents with Iodine:  Facile Low-Temperature McMurry Reaction and N/O-Debenzylation/Deallylation†
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    Bio-Organic Division, Bhabha Atomic Research Centre, Mumbai (Bombay)-400 085, India
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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 1998, 63, 15, 4925–4929
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    https://doi.org/10.1021/jo971751v
    Published July 7, 1998
    Copyright © 1998 American Chemical Society
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    Abstract

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    A highly reactive, low-valent titanium (LVT) reagent has been prepared by the addition of substoichiometric amounts of iodine to the LVT species generated by Rieke's method (TiCl3−Li−THF). While the conventional McMurry reaction requires high temperatures and prolonged reaction times for the generation of olefins, the present activated LVT reagent is able to effect the reductive coupling of aliphatic as well as aromatic carbonyls to the corresponding olefins at lower temperatures and much reduced reaction times. The protocol is also useful for the intramolecular coupling reactions leading to the one-step synthesis of heterocycles. The temperature-controlled McMurry reaction provides enhanced diastereoselectivity and features an excellent chemoselectivity. In addition to the McMurry reaction, other SET-induced carbon−heteroatom (O, N) bond cleavages can also be carried out with the activated reagent at a fast rate and at a low temperature in high yields.

    Copyright © 1998 American Chemical Society

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    †

     In respectful memory of the late Professor Sir Derek H. R. Barton.

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    In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 1998, 63, 15, 4925–4929
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jo971751v
    Published July 7, 1998
    Copyright © 1998 American Chemical Society
    Request reuse permissions

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