A phosphine-accelerated ArF-chloride bond activation process by palladium

Meital Orbach; Olena V. Zenkina; Yael Diskin Posner; Mark A. Iron; Milko E. van der Boom

doi:10.1021/om400295p

A phosphine-accelerated Ar_F-chloride bond activation process by palladium

Meital Orbach, Olena V. Zenkina, Yael Diskin Posner, Mark A. Iron, Milko E. van der Boom

Weizmann Institute of Science

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

Abstract

We present a mechanistic study demonstrating selective Ar_f-Cl bond activation preceded by η² coordination of Pd(PEt ₃)₂ to a C=C moiety of a partially fluorinated substrate. An intramolecular ring-walking process to activate the Ar_f-Cl bond is plausible, but an intermolecular reaction becomes dominant in the presence of PEt₃. The latter pathway is significantly enhanced, since PEt ₃ promotes dissociation of Pd(PEt₃)₃ from the C=C moiety followed by activation of the Ar_f-Cl bond. Our observations also show that PEt₃ can be used to control reaction selectivity. The experimental observations are supported by density functional theory (DFT) calculations (at the SMD(toluene)-DSD-PBEP86/cc-pV(D+d)Z-PP//DF- PBE+d_v2/SDD(d) level of theory).

Original language	English
Pages (from-to)	3074-3082
Number of pages	9
Journal	Organometallics
Volume	32
Issue number	10
DOIs	https://doi.org/10.1021/om400295p
State	Published - 24 May 2013

All Science Journal Classification (ASJC) codes

Inorganic Chemistry
Physical and Theoretical Chemistry
Organic Chemistry

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@article{3c087ef6f6aa4fa0b6e30809e39bace7,

title = "A phosphine-accelerated ArF-chloride bond activation process by palladium",

abstract = "We present a mechanistic study demonstrating selective Arf-Cl bond activation preceded by η2 coordination of Pd(PEt 3)2 to a C=C moiety of a partially fluorinated substrate. An intramolecular ring-walking process to activate the Arf-Cl bond is plausible, but an intermolecular reaction becomes dominant in the presence of PEt3. The latter pathway is significantly enhanced, since PEt 3 promotes dissociation of Pd(PEt3)3 from the C=C moiety followed by activation of the Arf-Cl bond. Our observations also show that PEt3 can be used to control reaction selectivity. The experimental observations are supported by density functional theory (DFT) calculations (at the SMD(toluene)-DSD-PBEP86/cc-pV(D+d)Z-PP//DF- PBE+dv2/SDD(d) level of theory).",

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

note = "Helen and Martin Kimmel Center for Molecular DesignThis research was supported by the Helen and Martin Kimmel Center for Molecular Design. We thank Dr. J. Choudhury for helpful discussions and Dr. L. J. W. Shimon for the X-ray analysis of complex 3 (WIS). M.v.d.B is the incumbent of the Bruce A. Pearlman Professorial Chair in Synthetic Organic Chemistry.",

year = "2013",

month = may,

day = "24",

doi = "10.1021/om400295p",

language = "الإنجليزيّة",

volume = "32",

pages = "3074--3082",

journal = "Organometallics",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - A phosphine-accelerated ArF-chloride bond activation process by palladium

AU - Orbach, Meital

AU - Zenkina, Olena V.

AU - Diskin Posner, Yael

AU - Iron, Mark A.

AU - van der Boom, Milko E.

N1 - Helen and Martin Kimmel Center for Molecular DesignThis research was supported by the Helen and Martin Kimmel Center for Molecular Design. We thank Dr. J. Choudhury for helpful discussions and Dr. L. J. W. Shimon for the X-ray analysis of complex 3 (WIS). M.v.d.B is the incumbent of the Bruce A. Pearlman Professorial Chair in Synthetic Organic Chemistry.

PY - 2013/5/24

Y1 - 2013/5/24

N2 - We present a mechanistic study demonstrating selective Arf-Cl bond activation preceded by η2 coordination of Pd(PEt 3)2 to a C=C moiety of a partially fluorinated substrate. An intramolecular ring-walking process to activate the Arf-Cl bond is plausible, but an intermolecular reaction becomes dominant in the presence of PEt3. The latter pathway is significantly enhanced, since PEt 3 promotes dissociation of Pd(PEt3)3 from the C=C moiety followed by activation of the Arf-Cl bond. Our observations also show that PEt3 can be used to control reaction selectivity. The experimental observations are supported by density functional theory (DFT) calculations (at the SMD(toluene)-DSD-PBEP86/cc-pV(D+d)Z-PP//DF- PBE+dv2/SDD(d) level of theory).

AB - We present a mechanistic study demonstrating selective Arf-Cl bond activation preceded by η2 coordination of Pd(PEt 3)2 to a C=C moiety of a partially fluorinated substrate. An intramolecular ring-walking process to activate the Arf-Cl bond is plausible, but an intermolecular reaction becomes dominant in the presence of PEt3. The latter pathway is significantly enhanced, since PEt 3 promotes dissociation of Pd(PEt3)3 from the C=C moiety followed by activation of the Arf-Cl bond. Our observations also show that PEt3 can be used to control reaction selectivity. The experimental observations are supported by density functional theory (DFT) calculations (at the SMD(toluene)-DSD-PBEP86/cc-pV(D+d)Z-PP//DF- PBE+dv2/SDD(d) level of theory).

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U2 - 10.1021/om400295p

DO - 10.1021/om400295p

M3 - مقالة

SN - 0276-7333

VL - 32

SP - 3074

EP - 3082

JO - Organometallics

JF - Organometallics

IS - 10

ER -

A phosphine-accelerated Ar_F-chloride bond activation process by palladium

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