TY - JOUR
T1 - Catalysis of Radical Cyclizations from Alkyl Iodides under H2
T2 - Evidence for Electron Transfer from [CpV(CO)3H]-
AU - Kuo, Jonathan L.
AU - Lorenc, Chris
AU - Abuyuan, Janine M.
AU - Norton, Jack R.
N1 - Funding Information:
Research reported in this publication was supported by the National Institute of General Medical Sciences of the National Institutes of Health under Award R01GM124295.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/4/4
Y1 - 2018/4/4
N2 - Radical cyclizations are most often achieved with Bu3SnH in the presence of a radical initiator, but environmental considerations demand that alternative reagents be developed - ones that can serve as a synthetic equivalent to the hydrogen atom. We have revisited [CpV(CO)3H]-, a known replacement for Bu3SnH, and found that it can be used catalytically under H2 in the presence of a base. We have carried out tin-free catalytic radical cyclizations of alkyl iodide substrates. The reactions are atom-efficient, and the conditions are mild, with broad tolerance for functional groups. We have, for example, achieved the first 5-exo radical cyclization involving attack onto a vinyl chloride. We suggest that the radicals are generated by an initial electron transfer.
AB - Radical cyclizations are most often achieved with Bu3SnH in the presence of a radical initiator, but environmental considerations demand that alternative reagents be developed - ones that can serve as a synthetic equivalent to the hydrogen atom. We have revisited [CpV(CO)3H]-, a known replacement for Bu3SnH, and found that it can be used catalytically under H2 in the presence of a base. We have carried out tin-free catalytic radical cyclizations of alkyl iodide substrates. The reactions are atom-efficient, and the conditions are mild, with broad tolerance for functional groups. We have, for example, achieved the first 5-exo radical cyclization involving attack onto a vinyl chloride. We suggest that the radicals are generated by an initial electron transfer.
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U2 - 10.1021/jacs.8b02119
DO - 10.1021/jacs.8b02119
M3 - Article
C2 - 29543448
AN - SCOPUS:85044933819
SN - 0002-7863
VL - 140
SP - 4512
EP - 4516
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 13
ER -