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 in | Angewandte Chemie International Edition Vol. 63; no. 18; pp. e202401050 - n/a |
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Main Authors | , , , , , , , , |
Format | Journal Article |
Language | English |
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Edition | International ed. in English |
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ISSN | 1433-7851 1521-3773 1521-3773 |
DOI | 10.1002/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. |
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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 |
Author_xml | – sequence: 1 givenname: Yi surname: Wei fullname: Wei, Yi organization: East China Normal University – sequence: 2 givenname: Xiao‐Yu surname: Xie fullname: Xie, Xiao‐Yu organization: East China Normal University – sequence: 3 givenname: Jiabin surname: Liu fullname: Liu, Jiabin organization: Zhengzhou University – sequence: 4 givenname: Xiaoxiao surname: Liu fullname: Liu, Xiaoxiao organization: Zhengzhou University – sequence: 5 givenname: Bo surname: Zhang fullname: Zhang, Bo organization: East China Normal University – sequence: 6 givenname: Xin‐Yi surname: Chen fullname: Chen, Xin‐Yi organization: East China Normal University – sequence: 7 givenname: Shi‐Jun orcidid: 0000-0001-9872-6245 surname: Li fullname: Li, Shi‐Jun email: lishijunzong@zzu.edu.cn organization: Zhengzhou University – sequence: 8 givenname: Yu orcidid: 0000-0002-2328-0020 surname: Lan fullname: Lan, Yu organization: Chongqing University – sequence: 9 givenname: Kai orcidid: 0000-0001-7341-4931 surname: Hong fullname: Hong, Kai email: khong@chem.ecnu.edu.cn organization: East China Normal University |
BackLink | https://www.ncbi.nlm.nih.gov/pubmed/38444397$$D View this record in MEDLINE/PubMed |
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CitedBy_id | crossref_primary_10_1016_j_mcat_2024_114733 crossref_primary_10_1002_anie_202415301 crossref_primary_10_1021_acs_orglett_4c03804 crossref_primary_10_1002_ejoc_202401396 crossref_primary_10_1021_acs_orglett_5c00259 crossref_primary_10_1021_acs_orglett_5c00469 crossref_primary_10_1039_D4SC06514J crossref_primary_10_1021_acs_orglett_4c04018 crossref_primary_10_1021_acs_orglett_4c02510 crossref_primary_10_1002_cjoc_202400840 crossref_primary_10_1002_chem_202401801 crossref_primary_10_1021_acs_orglett_4c04690 crossref_primary_10_1002_ange_202415301 |
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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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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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