Palladium-catalyzed cross-coupling reactions with fluorinated substrates: Mechanistic insights into the undesired hydrodehalogenation of aryl halides

Meital Orbach; Joyanta Choudhury; Michal Lahav; Olena V. Zenkina; Yael Diskin Posner; Gregory Leitus; Mark A. Iron; Milko E. van der Boom

doi:10.1021/om200898t

Palladium-catalyzed cross-coupling reactions with fluorinated substrates: Mechanistic insights into the undesired hydrodehalogenation of aryl halides

Meital Orbach, Joyanta Choudhury, Michal Lahav, Olena V. Zenkina, Yael Diskin Posner, Gregory Leitus, Mark A. Iron, Milko E. van der Boom

Weizmann Institute of Science

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

Abstract

We report here that the undesired hydrodehalogenation in cross-coupling reactions with fluorinated substrates involves water as a possible hydrogen source. Moreover, the product distribution (hydrodehalogenation vs carbon-carbon coupling) can be controlled by varying the phosphine substituents. Significant hydrodehalogenation occurs prior to the formation of Ar _F-Pd(II)-Br complexes. DFT calculations were used to evaluate a direct hydrodehalogenation route with a phosphine and water. These findings provide new mechanistic insight into aryl-Br bond activation with fluorinated substrates and selective arene functionalization.

Original language	English
Pages (from-to)	1271-1274
Number of pages	4
Journal	Organometallics
Volume	31
Issue number	4
DOIs	https://doi.org/10.1021/om200898t
State	Published - 27 Feb 2012

All Science Journal Classification (ASJC) codes

Inorganic Chemistry
Physical and Theoretical Chemistry
Organic Chemistry

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10.1021/om200898t

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title = "Palladium-catalyzed cross-coupling reactions with fluorinated substrates: Mechanistic insights into the undesired hydrodehalogenation of aryl halides",

abstract = "We report here that the undesired hydrodehalogenation in cross-coupling reactions with fluorinated substrates involves water as a possible hydrogen source. Moreover, the product distribution (hydrodehalogenation vs carbon-carbon coupling) can be controlled by varying the phosphine substituents. Significant hydrodehalogenation occurs prior to the formation of Ar F-Pd(II)-Br complexes. DFT calculations were used to evaluate a direct hydrodehalogenation route with a phosphine and water. These findings provide new mechanistic insight into aryl-Br bond activation with fluorinated substrates and selective arene functionalization.",

author = "Meital Orbach and Joyanta Choudhury and Michal Lahav and Zenkina, \{Olena V.\} and \{Diskin Posner\}, Yael and Gregory Leitus and Iron, \{Mark A.\} and \{van der Boom\}, \{Milko E.\}",

note = "Helen and Martin Kimmel Center for Molecular Design; EUThis research was supported by the Helen and Martin Kimmel Center for Molecular Design. J.C. thanks the EU (FP7 program) for an Incoming Marie Curie fellowship. Dr. A. C. B. Lucassen is acknowledged for his assistance. M.E.v.d.B. is the incumbent of the Bruce A. Pearlman Professorial Chair in Synthetic Organic Chemistry.",

year = "2012",

month = feb,

day = "27",

doi = "10.1021/om200898t",

language = "الإنجليزيّة",

volume = "31",

pages = "1271--1274",

journal = "Organometallics",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - Palladium-catalyzed cross-coupling reactions with fluorinated substrates

T2 - Mechanistic insights into the undesired hydrodehalogenation of aryl halides

AU - Orbach, Meital

AU - Choudhury, Joyanta

AU - Lahav, Michal

AU - Zenkina, Olena V.

AU - Diskin Posner, Yael

AU - Leitus, Gregory

AU - Iron, Mark A.

AU - van der Boom, Milko E.

N1 - Helen and Martin Kimmel Center for Molecular Design; EUThis research was supported by the Helen and Martin Kimmel Center for Molecular Design. J.C. thanks the EU (FP7 program) for an Incoming Marie Curie fellowship. Dr. A. C. B. Lucassen is acknowledged for his assistance. M.E.v.d.B. is the incumbent of the Bruce A. Pearlman Professorial Chair in Synthetic Organic Chemistry.

PY - 2012/2/27

Y1 - 2012/2/27

N2 - We report here that the undesired hydrodehalogenation in cross-coupling reactions with fluorinated substrates involves water as a possible hydrogen source. Moreover, the product distribution (hydrodehalogenation vs carbon-carbon coupling) can be controlled by varying the phosphine substituents. Significant hydrodehalogenation occurs prior to the formation of Ar F-Pd(II)-Br complexes. DFT calculations were used to evaluate a direct hydrodehalogenation route with a phosphine and water. These findings provide new mechanistic insight into aryl-Br bond activation with fluorinated substrates and selective arene functionalization.

AB - We report here that the undesired hydrodehalogenation in cross-coupling reactions with fluorinated substrates involves water as a possible hydrogen source. Moreover, the product distribution (hydrodehalogenation vs carbon-carbon coupling) can be controlled by varying the phosphine substituents. Significant hydrodehalogenation occurs prior to the formation of Ar F-Pd(II)-Br complexes. DFT calculations were used to evaluate a direct hydrodehalogenation route with a phosphine and water. These findings provide new mechanistic insight into aryl-Br bond activation with fluorinated substrates and selective arene functionalization.

UR - http://www.scopus.com/inward/record.url?scp=84857576057&partnerID=8YFLogxK

U2 - 10.1021/om200898t

DO - 10.1021/om200898t

M3 - مقالة

SN - 0276-7333

VL - 31

SP - 1271

EP - 1274

JO - Organometallics

JF - Organometallics

IS - 4

ER -

Palladium-catalyzed cross-coupling reactions with fluorinated substrates: Mechanistic insights into the undesired hydrodehalogenation of aryl halides

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All Science Journal Classification (ASJC) codes

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