Radical Isomerization and Cycloisomerization Initiated by H• Transfer

Gang Li; Jonathan L. Kuo; Arthur Han; Janine M. Abuyuan; Lily C. Young; Jack R. Norton; Joshua H. Palmer

doi:10.1021/jacs.6b03509

Radical Isomerization and Cycloisomerization Initiated by H• Transfer

Gang Li, Jonathan L. Kuo, Arthur Han, Janine M. Abuyuan, Lily C. Young, Jack R. Norton, Joshua H. Palmer

Chemistry

Research output: Contribution to journal › Article › peer-review

113 Scopus citations

Abstract

Under H₂ pressure, Co^II(dmgBF₂)₂L₂ (L = H₂O, THF) generates a low concentration of an H• donor. Transfer of the H• onto an olefin gives a radical that can either (1) transfer an H• back to the metal, generating an isomerized olefin, or (2) add intramolecularly to a double bond, generating a cyclized radical. Transfer of an H• back to the metal from the cyclized radical results in a cycloisomerization. Both outcomes are favored by the low concentration of the cobalt H• donor, whereas hydrogenation and cyclohydrogenation are more likely with other catalysts (when the concentration of the H• donor is high).

Original language	English (US)
Pages (from-to)	7698-7704
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	138
Issue number	24
DOIs	https://doi.org/10.1021/jacs.6b03509
State	Published - Jun 22 2016

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Radical Isomerization and Cycloisomerization Initiated by H• Transfer",

abstract = "Under H2 pressure, CoII(dmgBF2)2L2 (L = H2O, THF) generates a low concentration of an H• donor. Transfer of the H• onto an olefin gives a radical that can either (1) transfer an H• back to the metal, generating an isomerized olefin, or (2) add intramolecularly to a double bond, generating a cyclized radical. Transfer of an H• back to the metal from the cyclized radical results in a cycloisomerization. Both outcomes are favored by the low concentration of the cobalt H• donor, whereas hydrogenation and cyclohydrogenation are more likely with other catalysts (when the concentration of the H• donor is high).",

author = "Gang Li and Kuo, {Jonathan L.} and Arthur Han and Abuyuan, {Janine M.} and Young, {Lily C.} and Norton, {Jack R.} and Palmer, {Joshua H.}",

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T1 - Radical Isomerization and Cycloisomerization Initiated by H• Transfer

AU - Li, Gang

AU - Kuo, Jonathan L.

AU - Han, Arthur

AU - Abuyuan, Janine M.

AU - Young, Lily C.

AU - Norton, Jack R.

AU - Palmer, Joshua H.

PY - 2016/6/22

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N2 - Under H2 pressure, CoII(dmgBF2)2L2 (L = H2O, THF) generates a low concentration of an H• donor. Transfer of the H• onto an olefin gives a radical that can either (1) transfer an H• back to the metal, generating an isomerized olefin, or (2) add intramolecularly to a double bond, generating a cyclized radical. Transfer of an H• back to the metal from the cyclized radical results in a cycloisomerization. Both outcomes are favored by the low concentration of the cobalt H• donor, whereas hydrogenation and cyclohydrogenation are more likely with other catalysts (when the concentration of the H• donor is high).

AB - Under H2 pressure, CoII(dmgBF2)2L2 (L = H2O, THF) generates a low concentration of an H• donor. Transfer of the H• onto an olefin gives a radical that can either (1) transfer an H• back to the metal, generating an isomerized olefin, or (2) add intramolecularly to a double bond, generating a cyclized radical. Transfer of an H• back to the metal from the cyclized radical results in a cycloisomerization. Both outcomes are favored by the low concentration of the cobalt H• donor, whereas hydrogenation and cyclohydrogenation are more likely with other catalysts (when the concentration of the H• donor is high).

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Radical Isomerization and Cycloisomerization Initiated by H• Transfer

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