Cobalt-catalysed enantioselective C(sp3)–C(sp3) coupling

Li, Yan; Nie, Wan; Chang, Zhe; Wang, Jia-wang; Lü, Xi; Fu, Yao

doi:10.1038/s41929-021-00688-w

“…Based on the experimental results and literature precedence, [15, 16, 20, 21] possible mechanisms were proposed the regiodivergent hydroalkylations of alkenes and depicted in Figure 2. For Ni‐catalyzed regiodivergent hydroalkylations, Ni I ‐X ( A ) could be converted to Ni I ‐H species ( B ) in the presence of a base and a silane.…”

Section: Resultsmentioning

confidence: 99%

Orthogonal Access to α‐/β‐Branched/Linear Aliphatic Amines by Catalyst‐Tuned Regiodivergent Hydroalkylations

Yang

¹

,

Shu

²

2022

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Linear, α‐branched, and β‐branched aliphatic amines are widespread in pharmaceuticals, agrochemicals, and fine chemicals. Thus, the development of direct and efficient methods to these structures in a tunable manner is highly desirable yet challenging. Herein, a catalyst‐controlled synthesis of α‐branched, β‐branched and linear aliphatic amines from Ni/Co‐catalyzed regio‐ and site‐selective hydroalkylations of alkenyl amines with alkyl halides is developed. This catalytic protocol features the reliable prediction and control of the coupling position of alkylation to provide orthogonal access to α‐branched, β‐branched and linear alkyl amines from identical starting materials. This platform unlocks orthogonal reactivity and selectivity of nickel hydride and cobalt hydride chemistry to catalytically repurpose three types of alkyl amines under mild conditions.

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“…The intermediate I undergoes migratory insertion, radical rebound and reductive elimination sequentially to give terminal selective product (5) and Co I (G). [21] No directing effect is involved in the Co-catalysis and the terminal regioselectivity is controlled by the steric repulsion between ligated cobalt center and substituents on alkenes.…”

Section: Methodsmentioning

confidence: 99%

Orthogonal Access to α‐/β‐Branched/Linear Aliphatic Amines by Catalyst‐Tuned Regiodivergent Hydroalkylations

Yang

¹

,

Shu

²

2022

View full text Add to dashboard Cite

Linear, α‐branched, and β‐branched aliphatic amines are widespread in pharmaceuticals, agrochemicals, and fine chemicals. Thus, the development of direct and efficient methods to these structures in a tunable manner is highly desirable yet challenging. Herein, a catalyst‐controlled synthesis of α‐branched, β‐branched and linear aliphatic amines from Ni/Co‐catalyzed regio‐ and site‐selective hydroalkylations of alkenyl amines with alkyl halides is developed. This catalytic protocol features the reliable prediction and control of the coupling position of alkylation to provide orthogonal access to α‐branched, β‐branched and linear alkyl amines from identical starting materials. This platform unlocks orthogonal reactivity and selectivity of nickel hydride and cobalt hydride chemistry to catalytically repurpose three types of alkyl amines under mild conditions.

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“…In a recent example, Martin and co‐workers reported the discovery of the temperature‐dependent regiodivergent remote carboxylation of alkyl halides with carbon dioxide [15] . Inspired by these achievements and pursuing our interest in alkene hydroalkylation, [3b,d, 11d, 16] we sought to explore the influence of temperature on switchable site‐selectivity in alkene functionalization reactions. Herein, we report our discovery of a simple temperature switch for the regiochemical control of alkene functionalization reactions (Figure 1B).…”

Section: Introductionmentioning

confidence: 99%

Nickel‐Catalyzed Switchable Site‐Selective Alkene Hydroalkylation by Temperature Regulation**

Wang

¹

,

Liu

²

,

Chang

³

et al. 2022

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Regiodivergent alkene functionalization that produces either regioisomer starting from the same raw materials is desirable. Herein, we report a nickelcatalyzed switchable site-selective alkene hydroalkylation. The selection of reaction temperatures leads to protocols that provide regiodivergent hydroalkylated products starting from a single alkene substrate. This protocol allows the convenient synthesis of α-and βbranched protected amines, both of which are important to the fields of pharmaceutical chemistry and biochemistry. In addition, enantioenriched β-branched alkylamines can be accessed in a catalytic asymmetric variant. Preliminary mechanistic studies indicate that the formation of a more stable nickelacycle provides the driving force of migration. The thermodynamic and kinetic properties of different reduction elimination intermediates are responsible for the switchable siteselectivity.

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Cobalt-catalysed enantioselective C(sp3)–C(sp3) coupling

Cited by 85 publications

References 60 publications

Orthogonal Access to α‐/β‐Branched/Linear Aliphatic Amines by Catalyst‐Tuned Regiodivergent Hydroalkylations

Orthogonal Access to α‐/β‐Branched/Linear Aliphatic Amines by Catalyst‐Tuned Regiodivergent Hydroalkylations

Orthogonal Access to α‐/β‐Branched/Linear Aliphatic Amines by Catalyst‐Tuned Regiodivergent Hydroalkylations

Nickel‐Catalyzed Switchable Site‐Selective Alkene Hydroalkylation by Temperature Regulation**

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