Nickel‐Catalyzed Arylboration of Alkenylarenes: Synthesis of Boron‐Substituted Quaternary Carbons and Regiodivergent Reactions

During the past decade, many research groups have described catalytic methods for 1,2-carboboration, allowing access to structurally complex organoboronates from alkenes. Various transition metals, especially copper, palladium, and nickel, have been widely used in these reactions. This review summarizes advances in this field, with a special focus on the catalytic cycles involved in different metal-catalyzed carboboration reactions, as well as the regio-and stereochemical consequences of the underlying mechanisms. 1,2-Carboboration of other unsaturated systems, such as alkynes and allenes, is outside of the scope of this review. Scheme 1. General depiction of catalyst-controlled 1,2-carboboration. In this scheme and throughout the manuscript, nucleophilic reaction partners are drawn in blue, and electrophilic reaction partners are drawn in red. Scheme 4. Cu(I)-catalyzed borylative radical cyclization. Scheme 5. Cu(I)-catalyzed intramolecular carboboration involving an aldol cyclization. Scheme 6. Cu(I)-catalyzed intramolecular acylboration.Review Isr. J. Chem. 2020, 60, 219 -229 Scheme 7. Cu(I)-catalyzed divergent alkylboration of alkenes. Scheme 8. Cu(I)-catalyzed alkene carboboration with aldehydes as the electrophile. Scheme 9. Cu(I)-catalyzed three-component acylboration. Scheme 10. Cu(I)-catalyzed heteroarylboration of 1,3-dienes.

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“…Shortly after- wards, Brown and coworkers reported a method of 1,2arylboration of tri-and disubstituted vinyl arenes (Scheme 20). [40,41]…”

Section: Ni-catalyzed Alkene Carboborationmentioning

confidence: 99%

“…A variety of aryl halides were compatible electrophiles in this transformation. Shortly afterwards, Brown and coworkers reported a method of 1,2‐arylboration of tri‐ and disubstituted vinyl arenes (Scheme ) …”

Section: Transition‐metal‐catalyzed Alkene 12‐carboboration Reactionsmentioning

confidence: 99%

Transition‐Metal‐Catalyzed 1,2‐Carboboration of Alkenes: Strategies, Mechanisms, and Stereocontrol

Liu

Gao

Zeng

et al. 2019

Israel Journal of Chemistry

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Palladium(0)‐Catalyzed Directed syn‐1,2‐Carboboration and ‐Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol by a Chiral Auxiliary

Liu

et al. 2019

Angewandte Chemie

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We report the development of palladium(0)‐catalyzed syn‐selective 1,2‐carboboration and ‐silylation reactions of alkenes containing cleavable directing groups. With B2pin2 or PhMe2Si‐Bpin as nucleophiles and aryl/alkenyl triflates as electrophiles, a broad range of mono‐, di‐, tri‐ and tetrasubstituted alkenes are compatible in these transformations. We further describe a directed dearomative 1,2‐carboboration of electron‐rich heteroarenes by employing this approach. Through use of a removable chiral directing group, we demonstrate the viability of achieving stereoinduction in Heck‐type alkene 1,2‐difunctionalization. This work introduces new avenues to access highly functionalized boronates and silanes with precise regio‐ and stereocontrol.

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Iron‐Catalyzed Regioselective Alkenylboration of Olefins

Zheng

Zhao

et al. 2020

Angewandte Chemie

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The first examples of an iron-catalyzed threecomponent synthesis of homoallylic boronates from regioselective union of bis(pinacolato)diboron, an alkenyl halide (bromide, chloride or fluoride), and an olefin are disclosed. Products that bear tertiary or quaternary carbon centers could be generated in up to 87 % yield as single regioisomers with complete retention of the olefin stereochemistry. With cyclopropylidene-containing substrates, ring cleavage leading to trisubstituted E-alkenylboronates were selectively obtained. Mechanistic studies revealed reaction attributes that are distinct from previously reported alkene carboboration pathways.

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Nickel‐Catalyzed Arylboration of Alkenylarenes: Synthesis of Boron‐Substituted Quaternary Carbons and Regiodivergent Reactions

Abstract: Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.

Cited by 14 publications

References 56 publications

Transition‐Metal‐Catalyzed 1,2‐Carboboration of Alkenes: Strategies, Mechanisms, and Stereocontrol

Transition‐Metal‐Catalyzed 1,2‐Carboboration of Alkenes: Strategies, Mechanisms, and Stereocontrol

Palladium(0)‐Catalyzed Directed syn‐1,2‐Carboboration and ‐Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol by a Chiral Auxiliary

Iron‐Catalyzed Regioselective Alkenylboration of Olefins

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