Speciation control during Suzuki-Miyaura cross-coupling of haloaryl and haloalkenyl MIDA boronic esters

James W. B. Fyfe; Elena Valverde; Ciaran P. Seath; Alan R. Kennedy; Joanna M. Redmond; Niall A. Anderson; Allan J. B.  Watson

doi:10.1002/chem.201500970

Speciation control during Suzuki-Miyaura cross-coupling of haloaryl and haloalkenyl MIDA boronic esters

James W. B. Fyfe, Elena Valverde, Ciaran P. Seath, Alan R. Kennedy, Joanna M. Redmond, Niall A. Anderson, Allan J. B. Watson

Pure And Applied Chemistry

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Abstract

Boronic acid solution speciation can be controlled during the Suzuki-Miyaura cross-coupling of haloaryl MIDA boronic esters to enable the formal homologation of boronic acid derivatives. The reaction is contingent upon control of the basic biphase and is thermodynamically driven: temperature control provides highly chemoselective access to either BMIDA adducts at room temperature or BPin products at elevated temperature. Control experiments and solubility analyses have provided some insight into the mechanistic operation of the formal homologation process.

Original language	English
Pages (from-to)	8951–8964
Number of pages	14
Journal	Chemistry - A European Journal
Volume	21
Issue number	24
Early online date	8 May 2015
DOIs	https://doi.org/10.1002/chem.201500970
Publication status	Published - 8 Jun 2015

Keywords

boron
chemoselectivity
cross-coupling
palladium
speciation

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10.1002/chem.201500970

Fyfe-etal-CAEJ-2015-Speciation-control-during-Suzuki-Miyaura-cross-coupling-of-haloarylAccepted author manuscript, 1.99 MB

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@article{8ab91224b16046a3bb40a73e8418bd4a,

title = "Speciation control during Suzuki-Miyaura cross-coupling of haloaryl and haloalkenyl MIDA boronic esters",

abstract = "Boronic acid solution speciation can be controlled during the Suzuki-Miyaura cross-coupling of haloaryl MIDA boronic esters to enable the formal homologation of boronic acid derivatives. The reaction is contingent upon control of the basic biphase and is thermodynamically driven: temperature control provides highly chemoselective access to either BMIDA adducts at room temperature or BPin products at elevated temperature. Control experiments and solubility analyses have provided some insight into the mechanistic operation of the formal homologation process.",

keywords = "boron, chemoselectivity, cross-coupling, palladium, speciation",

author = "Fyfe, \{James W. B.\} and Elena Valverde and Seath, \{Ciaran P.\} and Kennedy, \{Alan R.\} and Redmond, \{Joanna M.\} and Anderson, \{Niall A.\} and Watson, \{Allan J. B.\}",

note = " This is the peer reviewed version of the following article: Fyfe, J. W. B., Valverde, E., Seath, C. P., Kennedy, A. R., Redmond, J. M., Anderson, N. A., \& Watson, A. J. B. (2015). Speciation control during Suzuki-Miyaura cross-coupling of haloaryl and haloalkenyl MIDA boronic esters. Chemistry - A European Journal, 21(24), 8951–8964, which has been published in final form at http://dx.doi.org/10.1002/chem.201500970 This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving",

year = "2015",

month = jun,

day = "8",

doi = "10.1002/chem.201500970",

language = "English",

volume = "21",

pages = "8951–8964",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley and Sons Inc.",

number = "24",

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TY - JOUR

T1 - Speciation control during Suzuki-Miyaura cross-coupling of haloaryl and haloalkenyl MIDA boronic esters

AU - Fyfe, James W. B.

AU - Valverde, Elena

AU - Seath, Ciaran P.

AU - Kennedy, Alan R.

AU - Redmond, Joanna M.

AU - Anderson, Niall A.

AU - Watson, Allan J. B.

N1 - This is the peer reviewed version of the following article: Fyfe, J. W. B., Valverde, E., Seath, C. P., Kennedy, A. R., Redmond, J. M., Anderson, N. A., & Watson, A. J. B. (2015). Speciation control during Suzuki-Miyaura cross-coupling of haloaryl and haloalkenyl MIDA boronic esters. Chemistry - A European Journal, 21(24), 8951–8964, which has been published in final form at http://dx.doi.org/10.1002/chem.201500970 This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving

PY - 2015/6/8

Y1 - 2015/6/8

N2 - Boronic acid solution speciation can be controlled during the Suzuki-Miyaura cross-coupling of haloaryl MIDA boronic esters to enable the formal homologation of boronic acid derivatives. The reaction is contingent upon control of the basic biphase and is thermodynamically driven: temperature control provides highly chemoselective access to either BMIDA adducts at room temperature or BPin products at elevated temperature. Control experiments and solubility analyses have provided some insight into the mechanistic operation of the formal homologation process.

AB - Boronic acid solution speciation can be controlled during the Suzuki-Miyaura cross-coupling of haloaryl MIDA boronic esters to enable the formal homologation of boronic acid derivatives. The reaction is contingent upon control of the basic biphase and is thermodynamically driven: temperature control provides highly chemoselective access to either BMIDA adducts at room temperature or BPin products at elevated temperature. Control experiments and solubility analyses have provided some insight into the mechanistic operation of the formal homologation process.

KW - boron

KW - chemoselectivity

KW - cross-coupling

KW - palladium

KW - speciation

UR - http://onlinelibrary.wiley.com/journal/10.1002/%28ISSN%291521-3765;jsessionid=29C28E83F0F8CA7ADFC141D26650FFCE.f04t02

U2 - 10.1002/chem.201500970

DO - 10.1002/chem.201500970

M3 - Article

SN - 0947-6539

VL - 21

SP - 8951

EP - 8964

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 24

ER -

Speciation control during Suzuki-Miyaura cross-coupling of haloaryl and haloalkenyl MIDA boronic esters

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Speciation control during Suzuki-Miyaura cross-coupling of haloaryl and haloalkenyl MIDA boronic esters

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