<scp>Transition‐Metal‐Catalyzed</scp> Synthesis of Chiral Allylboronates<sup>†</sup>

Ming, Wenbo; Liu, Xiaocui; Mao, Lujia; Gu, Xiao; Ye, Qing

doi:10.1002/cjoc.202000708

Cited by 10 publications

(2 citation statements)

References 114 publications

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“…Chiral allylboronates have been widely utilized as key intermediates in the synthesis of a myriad of pharmaceutically interesting molecules. , Although alkenyl halides share similarities with aryl halides, some adjustments to the reaction conditions were needed to achieve satisfactory outcomes. Remarkably, this protocol accommodates alkenyl bromides with various substitution patterns …”

Section: 1-carboboration Of Terminal Alkenesmentioning

confidence: 99%

Nickel Chain-Walking Catalysis: A Journey to Migratory Carboboration of Alkenes

Li,

Yin

2023

Acc. Chem. Res.

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Conspectus Chain-walking offers extensive opportunities for innovating synthetic methods that involve constructing chemical bonds at unconventional sites. This approach provides previously inaccessible retrosynthetic disconnections in organic synthesis. Through chain-walking, transition metal-catalyzed alkene difunctionalization reactions can take place in a 1,n-addition (n ≠ 2) mode. Unlike classical 1,2-regioselective difunctionalization reactions, there remains a scarcity of reports regarding migratory patterns. Moreover, the range of olefins utilized in these studies is quite limited. About five years ago, our research group embarked on a project aimed at developing valuable migratory difunctionalization reactions of alkenes through chain-walking. Our focus was on carboboration of alkenes utilizing nickel catalysis. The reaction commences with the migratory insertion of an olefin into a Ni–Bpin species. Subsequently, a thermodynamically stable alkyl nickel complex is generated through a chain-walking process. This complex then couples with a carbon-based electrophile, leading to the formation of an alkylboron compound. It is worth highlighting that the success of these transformations relies significantly on the utilization of a bisnitrogen-based ligand and LiOMe as a B2pin2 activator. Synthetically, these migratory carboboration reactions establish a robust platform for the rapid and efficient synthesis of a wide range of structurally diverse organoboron compounds, which are not facially accessed by conventional methods. The incorporation of a versatile boron group introduces a wealth of possibilities for subsequent diversifications, significantly enhancing the value of the resulting products and allowing for the creation of a broader range of valuable derivatives and applications. This Account provides a comprehensive overview of our research efforts and advancements in the field of migratory carboboration of unactivated alkenes using nickel catalysis. We begin by outlining the development of a series of 1,1-regioselective carboboration reactions of terminal alkenes. A significant focus is placed on the initial integration of boronate, which not only triggers the formation of thermodynamically stable metal species but also exerts control over remote stereochemistry in reactions involving substituted methylenecyclohexenes. Continuing our exploration, remarkable success is achieved in 1,3-regio- and cis-stereoselectivity when dealing with cyclic alkenes. Remarkably, nickel chain-walking catalysis enables heterocyclic alkenes to be viable coupling partners within our transformations. Moreover, it grants us the ability to achieve regioselectivity for cyclohexenes that was previously unattainable, thus expanding the horizons of regiochemical control in these reactions. Lastly, we present the evolution of ligand-modulated regiodivergent carboboration of allylarenes. By gaining insights into the underlying mechanisms driving regiodivergence, we lay a strong foundation for tackling challenges related to selecting s...

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Section: 1-carboboration Of Terminal Alkenesmentioning

confidence: 99%

Nickel Chain-Walking Catalysis: A Journey to Migratory Carboboration of Alkenes

Li,

Yin

2023

Acc. Chem. Res.

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“…Generally, the β-position of 1,3-dienes possesses higher reactivity than the δ-position due to the poor transmission of the electronic effect through the conjugated π-system [8], thus making it challenge to go through 1,6-additions [9]. Several strategies have been developed to achieve 1,6-conjugate addition with a number of different nucleophiles, such as highly active carbon nucleophilic reagents, organometallic reagents, and heteroatomic nucleophiles [10][11][12][13][14][15]. 1,6-Addition of carbonyl to extended Michael acceptors can yield useful products, such as 1,6-dicarbonyl compounds.…”

mentioning

confidence: 99%

Photoredox deoxygenative allylation of carboxylic acids via selective 1,6-addition of acyl radicals to electron-deficient 1,3-dienes

Zhang

Guo

et al. 2023

Chinese Journal of Catalysis

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Stereoconvergent Access to Z‐Allylborons from E/Z‐Mixed 1,3‐Dienes via Cu‐Guanidine Catalysis

Zhang,

Jin

et al. 2024

Adv Synth Catal

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Merging the stereoisomeric mixture of substrate into a single product through stereospecific transformation is a challenging but higher‐order synthetic strategy, which perfectly meets the demand of cost control in the precise chemical production. In this work, the stereoconvergent synthesis of Z‐allylic boronates was realized with protoborylation of E/Z‐mixed 1,3‐dienes catalyzed by a novel copper‐guanidine complex. The reaction could proceed smoothly under very mild conditions with good functional group tolerance, and convert diverse aryl‐substituted 1,3‐dienes into the desired Z‐1,4‐addition products with excellent chemo‐, regio‐, and stereoselectivities in minutes. Detailed mechanistic studies also helped to disclose the origin of stereoconvergency. Both E‐ and Z‐diene were found directly undergoing a rapid borylation without E/Z isomerization of C=C bond, followed by a convergent formation of the same thermodynamically stable allylcopper intermediate before the slow protonation step occurred.

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Transition‐Metal‐Catalyzed Synthesis of Chiral Allylboronates^†

Abstract: on the occasion of her 10th founding anniversary.

Cited by 10 publications

References 114 publications

Nickel Chain-Walking Catalysis: A Journey to Migratory Carboboration of Alkenes

Nickel Chain-Walking Catalysis: A Journey to Migratory Carboboration of Alkenes

Photoredox deoxygenative allylation of carboxylic acids via selective 1,6-addition of acyl radicals to electron-deficient 1,3-dienes

Stereoconvergent Access to Z‐Allylborons from E/Z‐Mixed 1,3‐Dienes via Cu‐Guanidine Catalysis

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Transition‐Metal‐Catalyzed Synthesis of Chiral Allylboronates†

Abstract: on the occasion of her 10th founding anniversary.

Cited by 10 publications

References 114 publications

Nickel Chain-Walking Catalysis: A Journey to Migratory Carboboration of Alkenes

Nickel Chain-Walking Catalysis: A Journey to Migratory Carboboration of Alkenes

Photoredox deoxygenative allylation of carboxylic acids via selective 1,6-addition of acyl radicals to electron-deficient 1,3-dienes

Stereoconvergent Access to Z‐Allylborons from E/Z‐Mixed 1,3‐Dienes via Cu‐Guanidine Catalysis

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Transition‐Metal‐Catalyzed Synthesis of Chiral Allylboronates^†