Palladium-Catalyzed, Site-Selective Direct Allylation of Aryl C-H Bonds by Silver-Mediated C-H Activation: A Synthetic and Mechanistic Investigation

Sarah Yunmi Lee; John F. Hartwig

doi:10.1021/jacs.6b10220

Palladium-Catalyzed, Site-Selective Direct Allylation of Aryl C-H Bonds by Silver-Mediated C-H Activation: A Synthetic and Mechanistic Investigation

Sarah Yunmi Lee, John F. Hartwig

Department of Chemistry

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

108 Citations (Scopus)

Abstract

We describe a method for the site-selective construction of a C(aryl)-C(sp³) bond by the palladium-catalyzed direct allylation of arenes with allylic pivalates in the presence of AgOPiv to afford the linear (E)-allylated arene with excellent regioselectivity; this reaction occurs with arenes that have not undergone site-selective and stereoselective direct allylation previously, such as monofluorobenzenes and non-fluorinated arenes. Mechanistic studies indicate that AgOPiv ligated by a phosphine reacts with the arene to form an arylsilver(I) species, presumably through a concerted metalation-deprotonation pathway. The activated aryl moiety is then transferred to an allylpalladium(II) intermediate formed by oxidative addition of the allylic pivalate to the Pd(0) complex. Subsequent reductive elimination furnishes the allyl-aryl coupled product. The aforementioned proposed intermediates, including an arylsilver complex, have been isolated, structurally characterized, and determined to be chemically and kinetically competent to undergo the proposed elementary steps of the catalytic cycle.

Original language	English
Pages (from-to)	15278-15284
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	138
Issue number	46
DOIs	https://doi.org/10.1021/jacs.6b10220
Publication status	Published - 2016 Nov 23

Bibliographical note

Funding Information:
This work was supported by the Director, Office of Science, of the U.S. Department of Energy under contract no. DE-AC02-05CH11231 and the National Institutes of Health (postdoctoral fellowship to S.Y.L.: F32-GM113404). We thank Dr. Antonio DiPasquale for X-ray crystallographic analysis (NIH Shared Instrumentation Grant S10-RR027172) and Thomas J. OConnor (supported by UC Berkeley Amgen Scholars program and CENTC program) for assistance on the initial investigation.

Publisher Copyright:
© 2016 American Chemical Society.

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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abstract = "We describe a method for the site-selective construction of a C(aryl)-C(sp3) bond by the palladium-catalyzed direct allylation of arenes with allylic pivalates in the presence of AgOPiv to afford the linear (E)-allylated arene with excellent regioselectivity; this reaction occurs with arenes that have not undergone site-selective and stereoselective direct allylation previously, such as monofluorobenzenes and non-fluorinated arenes. Mechanistic studies indicate that AgOPiv ligated by a phosphine reacts with the arene to form an arylsilver(I) species, presumably through a concerted metalation-deprotonation pathway. The activated aryl moiety is then transferred to an allylpalladium(II) intermediate formed by oxidative addition of the allylic pivalate to the Pd(0) complex. Subsequent reductive elimination furnishes the allyl-aryl coupled product. The aforementioned proposed intermediates, including an arylsilver complex, have been isolated, structurally characterized, and determined to be chemically and kinetically competent to undergo the proposed elementary steps of the catalytic cycle.",

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note = "Funding Information: This work was supported by the Director, Office of Science, of the U.S. Department of Energy under contract no. DE-AC02-05CH11231 and the National Institutes of Health (postdoctoral fellowship to S.Y.L.: F32-GM113404). We thank Dr. Antonio DiPasquale for X-ray crystallographic analysis (NIH Shared Instrumentation Grant S10-RR027172) and Thomas J. OConnor (supported by UC Berkeley Amgen Scholars program and CENTC program) for assistance on the initial investigation. Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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N2 - We describe a method for the site-selective construction of a C(aryl)-C(sp3) bond by the palladium-catalyzed direct allylation of arenes with allylic pivalates in the presence of AgOPiv to afford the linear (E)-allylated arene with excellent regioselectivity; this reaction occurs with arenes that have not undergone site-selective and stereoselective direct allylation previously, such as monofluorobenzenes and non-fluorinated arenes. Mechanistic studies indicate that AgOPiv ligated by a phosphine reacts with the arene to form an arylsilver(I) species, presumably through a concerted metalation-deprotonation pathway. The activated aryl moiety is then transferred to an allylpalladium(II) intermediate formed by oxidative addition of the allylic pivalate to the Pd(0) complex. Subsequent reductive elimination furnishes the allyl-aryl coupled product. The aforementioned proposed intermediates, including an arylsilver complex, have been isolated, structurally characterized, and determined to be chemically and kinetically competent to undergo the proposed elementary steps of the catalytic cycle.

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Palladium-Catalyzed, Site-Selective Direct Allylation of Aryl C-H Bonds by Silver-Mediated C-H Activation: A Synthetic and Mechanistic Investigation

Abstract

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