Palladium‐Catalyzed Cascade Heck Coupling and Allylboration of Iododiboron Compounds via Diboryl Radicals

Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles in the previous reports, however, has restrained their synthetic potential. Herein we disclose the ambiphilic reactivity of α‐halogenated geminal bis(boronates)...

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Published inAngewandte Chemie International Edition Vol. 63; no. 18; pp. e202401050 - n/a
Main Authors Wei, Yi, Xie, Xiao‐Yu, Liu, Jiabin, Liu, Xiaoxiao, Zhang, Bo, Chen, Xin‐Yi, Li, Shi‐Jun, Lan, Yu, Hong, Kai
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 24.04.2024
Wiley Subscription Services, Inc
EditionInternational ed. in English
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Online AccessGet full text
ISSN1433-7851
1521-3773
1521-3773
DOI10.1002/anie.202401050

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Abstract Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles in the previous reports, however, has restrained their synthetic potential. Herein we disclose the ambiphilic reactivity of α‐halogenated geminal bis(boronates), of which the first catalytic utilization was accomplished by merging a formal Heck cross‐coupling with a highly diastereoselective allylboration of aldehydes or imines, providing a new avenue for rapid assembly of polyfunctionalized boron‐containing compounds. We demonstrated that this cascade reaction is highly efficient and compatible with various functional groups, and a wide range of heterocycles. In contrast to a classical Pd(0/II) scenario, mechanistic experiments and DFT calculations have provided strong evidence for a catalytic cycle involving Pd(I)/diboryl carbon radical intermediates. The ambiphilic reactivity of iododiboron compounds was disclosed by palladium‐catalyzed three‐component reactions of iododiborons, alkenes and aldehydes/imines. The reaction features mild conditions, broad scope, excellent diastereoselectivity and functional group tolerance. An unconventional Pd(0/I/II) catalytic cycle is operative, supported by mechanistic experiments and DFT calculations.
AbstractList Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles in the previous reports, however, has restrained their synthetic potential. Herein we disclose the ambiphilic reactivity of α-halogenated geminal bis(boronates), of which the first catalytic utilization was accomplished by merging a formal Heck cross-coupling with a highly diastereoselective allylboration of aldehydes or imines, providing a new avenue for rapid assembly of polyfunctionalized boron-containing compounds. We demonstrated that this cascade reaction is highly efficient and compatible with various functional groups, and a wide range of heterocycles. In contrast to a classical Pd(0/II) scenario, mechanistic experiments and DFT calculations have provided strong evidence for a catalytic cycle involving Pd(I)/diboryl carbon radical intermediates.
Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles in the previous reports, however, has restrained their synthetic potential. Herein we disclose the ambiphilic reactivity of α-halogenated geminal bis(boronates), of which the first catalytic utilization was accomplished by merging a formal Heck cross-coupling with a highly diastereoselective allylboration of aldehydes or imines, providing a new avenue for rapid assembly of polyfunctionalized boron-containing compounds. We demonstrated that this cascade reaction is highly efficient and compatible with various functional groups, and a wide range of heterocycles. In contrast to a classical Pd(0/II) scenario, mechanistic experiments and DFT calculations have provided strong evidence for a catalytic cycle involving Pd(I)/diboryl carbon radical intermediates.Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles in the previous reports, however, has restrained their synthetic potential. Herein we disclose the ambiphilic reactivity of α-halogenated geminal bis(boronates), of which the first catalytic utilization was accomplished by merging a formal Heck cross-coupling with a highly diastereoselective allylboration of aldehydes or imines, providing a new avenue for rapid assembly of polyfunctionalized boron-containing compounds. We demonstrated that this cascade reaction is highly efficient and compatible with various functional groups, and a wide range of heterocycles. In contrast to a classical Pd(0/II) scenario, mechanistic experiments and DFT calculations have provided strong evidence for a catalytic cycle involving Pd(I)/diboryl carbon radical intermediates.
Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles in the previous reports, however, has restrained their synthetic potential. Herein we disclose the ambiphilic reactivity of α‐halogenated geminal bis(boronates), of which the first catalytic utilization was accomplished by merging a formal Heck cross‐coupling with a highly diastereoselective allylboration of aldehydes or imines, providing a new avenue for rapid assembly of polyfunctionalized boron‐containing compounds. We demonstrated that this cascade reaction is highly efficient and compatible with various functional groups, and a wide range of heterocycles. In contrast to a classical Pd(0/II) scenario, mechanistic experiments and DFT calculations have provided strong evidence for a catalytic cycle involving Pd(I)/diboryl carbon radical intermediates. The ambiphilic reactivity of iododiboron compounds was disclosed by palladium‐catalyzed three‐component reactions of iododiborons, alkenes and aldehydes/imines. The reaction features mild conditions, broad scope, excellent diastereoselectivity and functional group tolerance. An unconventional Pd(0/I/II) catalytic cycle is operative, supported by mechanistic experiments and DFT calculations.
Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles in the previous reports, however, has restrained their synthetic potential. Herein we disclose the ambiphilic reactivity of alpha-halogenated geminal bis(boronates), of which the first catalytic utilization was accomplished by merging a formal Heck cross-coupling with a highly diastereoselective allylboration of aldehydes or imines, providing a new avenue for rapid assembly of polyfunctionalized boron-containing compounds. We demonstrated that this cascade reaction is highly efficient and compatible with various functional groups, and a wide range of heterocycles. In contrast to a classical Pd(0/II) scenario, mechanistic experiments and DFT calculations have provided strong evidence for a catalytic cycle involving Pd(I)/diboryl carbon radical intermediates. The ambiphilic reactivity of iododiboron compounds was disclosed by palladium-catalyzed three-component reactions of iododiborons, alkenes and aldehydes/imines. The reaction features mild conditions, broad scope, excellent diastereoselectivity and functional group tolerance. An unconventional Pd(0/I/II) catalytic cycle is operative, supported by mechanistic experiments and DFT calculations.+ image
Author Li, Shi‐Jun
Hong, Kai
Liu, Jiabin
Xie, Xiao‐Yu
Zhang, Bo
Chen, Xin‐Yi
Lan, Yu
Wei, Yi
Liu, Xiaoxiao
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  email: khong@chem.ecnu.edu.cn
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Issue 18
Keywords GEM-DIBORYLALKANES
REAGENTS
ENANTIOSELECTIVE SYNTHESIS
Multicomponent Reaction
Iododiboron
STEREOSELECTIVE CROTYLATION
SUBSTITUTION-REACTIONS
ALKYL-HALIDES
Ambiphilic Reagent
Synthetic Methods
Organoboron
DIASTEREOSELECTIVE SYNTHESIS
ALPHA-BORYL CARBANIONS
ESTERS
ALLYLIC SUBSTITUTION
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2014; 16
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2024; 63
2013; 113
1968; 90
2024; 24
2022; 604
2014; 50
2006; 128
2014; 53
2021; 8
2023; 10
1995; 95
2007; 129
2015; 17
2023; 14
2015; 5
2018; 140
2011
2020; 142
2015; 54
2009
2014; 47
2021; 143
2021; 50
2024; 14
2019; 141
2018; 20
2011; 133
2003; 76
2017; 139
2014; 43
2016; 55
2022; 144
2021; 57
2023; 43
2017; 53
2010; 49
2021; 54
2012; 112
2021; 12
2021; 11
2022; 61
2002; 124
1997; 36
1999; 38
2022; 9
2019; 48
2011; 50
2017; 56
2010; 132
1988; 21
2020; 26
2013; 135
2017; 19
2015
2020; 22
2021; 60
2009; 109
2018; 16
2018; 59
2018; 57
1972; 37
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Snippet Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles in the previous...
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crossref
wiley
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StartPage e202401050
SubjectTerms Aldehydes
Ambiphilic Reagent
Boron
Cascade chemical reactions
Chemistry
Chemistry, Multidisciplinary
Cross coupling
Functional groups
Imines
Intermediates
Iododiboron
Multicomponent Reaction
Nucleophiles
Organic chemistry
Organoboron
Palladium
Physical Sciences
Science & Technology
Stereoselectivity
Synthetic Methods
Title Palladium‐Catalyzed Cascade Heck Coupling and Allylboration of Iododiboron Compounds via Diboryl Radicals
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https://www.ncbi.nlm.nih.gov/pubmed/38444397
https://www.proquest.com/docview/3040491111
https://www.proquest.com/docview/2938284095
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