Site-Selective Ni-Catalyzed Reductive Coupling of α-Haloboranes with Unactivated Olefins

Sun, Shang‐Zheng; Börjesson, Marino; Martín-Montero, Raúl; Martı́n, Rubén

doi:10.1021/jacs.8b09425

Cited by 234 publications

(61 citation statements)

References 59 publications

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“…The coupling was inhibited by the presence of a significant amount of TEMPO (see Section 6.3 in the Supporting Information). These results are consistent with the involvement of alkyl radicals in the hydroalkylation, which agrees with literature reports ––…”

Section: Methodssupporting

confidence: 94%

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Ligand‐Controlled Regiodivergent Hydroalkylation of Pyrrolines

Qian

2019

Angew Chem Int Ed

107

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Nickel hydride (NiH) catalyzed hydrocarbonation has emerged as an efficient approach to construct new C−C bonds containing at least one C(sp3) center. However, the regioselectivity of this reaction is by far dictated by substrates. Described here is a strategy to achieve two different regioselectivites of hydroalkylation of the same substrates by using ligand control. This strategy enables the first regiodivergent hydroalkylation of 3‐pyrrolines, yielding both 2‐ and 3‐alkylated pyrrolidines, valuable synthetic intermediates and common motifs in many bioactive molecules. This method demonstrates broad scope and high functional‐group tolerance, and can be applied in late‐stage functionalizations.

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Section: Methodssupporting

confidence: 94%

“…Recently, Martin and co‐workers reported a novel method for hydroalkylation of 3‐pyrolline with α‐haloboranes. However, the method was only C2 selective . To our knowledge, C3 selectivity remained elusive prior to our work.…”

Section: Methodsmentioning

confidence: 97%

Ligand‐Controlled Regiodivergent Hydroalkylation of Pyrrolines

Qian

2019

Angew Chem Int Ed

107

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“…Recent work utilizing Ni(bipyridine) complexes as catalysts in the presence of silane are believed to generate a Ni-hydride species that allows for reductive coupling reactions of alkenes to afford alkane products. Martin 28 and Hu 29 have reported the reductive coupling of alkyl halides and alkenes to afford boryl alkanes and substituted pyrrolidines, respectively (Scheme 7). Hydrometalation of the alkene by a Nihydride leads to an (alkyl)Ni species that can undergo chain-walking and cross-coupling with the alkyl electrophile 26 or 29 to furnish the observed products 28 and 31, respectively.…”

Section: Short Review Syn Thesismentioning

confidence: 99%

Recent Developments in C–C Bond Formation Using Catalytic Reductive Coupling Strategies

Agrawal

Sieber²

2020

Synthesis

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Metal-catalyzed reductive coupling processes have emerged as a powerful methodology for the introduction of molecular complexity from simple starting materials. These methods allow for an orthogonal approach to that of redox-neutral strategies for the formation of C–C bonds by enabling cross-coupling of starting materials not applicable to redox-neutral chemistry. This short review summarizes the most recent developments in the area of metal-catalyzed reductive coupling utilizing catalyst turnover by a stoichiometric reductant that becomes incorporated in the final product.1 Introduction2 Ni Catalysis3 Cu Catalysis4 Ru, Rh, and Ir Catalysis4.1 Alkenes4.2 1,3-Dienes4.3 Allenes4.4 Alkynes4.5 Enynes5 Fe, Co, and Mn Catalysis6 Conclusion and Outlook

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“…Our group has studied whether stabilized α‐boryl radical intermediates, generated by addition of electron‐rich radicals to vinylB(pin), might be intercepted with chiral nickel complexes that would allow subsequent stereoselective C–C bond formation . While the ability of Ni complexes to selectively combine with α‐boryl radicals had precedent from Ni‐catalyzed cross‐couplings of α‐haloboronates developed by Fu and Martin; it wasn't clear whether the transient radicals needed for the radical addition reaction would be intercepted by Ni complexes prematurely and preclude reaction with vinylB(pin). As can be seen in Scheme , when alkyl iodides, vinylB(pin) and organozinc reagents are treated with a chiral Ni/diamine complex, efficient and enantioselective radical addition/C‐C coupling can be achieved.…”

Section: Addition Of Electron‐rich Radicals To Electron‐deficient mentioning

confidence: 99%

Recent Advances in Radical Addition to Alkenylboron Compounds

Lovinger

Morken

2019

Eur J Org Chem

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The addition of carbon-centered radicals to alkenylboron compounds provides a useful method for the construction of organoboron reagents which are versatile reagents in chemical synthesis. While the first examples of this type or process appeared 70 years ago, until recently, attention to this type [a] G. Scheme 7. Aggarwal′s photoredox-catalyzed radical addition of carboxylic acids to alkenylboron reagents. Conditions: RCO 2 H, 1 % Ir catayst, 1.1 equiv. Cs 2 CO 3 , DMF, 35°C, 40 W blue LED.reductant furnishes an Fe-H species that undergoes H atom transfer; subsequent conjugate addition of the α-boryl radical to an activated alkene allowed C-C bond formation with a second reactant (Scheme 8). Interestingly, the reaction operates smoothly with both three-coordinate alkenylB(pin) derivatives as well as four-coordinate alkenylB(mida) compounds. According to the proposed mechanism, it is plausible that the two types of alkenylboron compounds react by different paths, with the non-stabilized α-boryl radical (8, BL 2 = mida) reacting as shown in Scheme 8, but the stabilized radical (8, L 2 = pin) undergoing reduction to an α-boryl carbanion prior to engaging in direct conjugate addition to give 10. [20] Scheme 8. Baran′s hydrogen-atom-transfer/radical conjugate addition involving alkenylboron compounds.Our group has studied whether stabilized α-boryl radical intermediates, generated by addition of electron-rich radicals to vinylB(pin), might be intercepted with chiral nickel complexes Eur.

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Site-Selective Ni-Catalyzed Reductive Coupling of α-Haloboranes with Unactivated Olefins

Cited by 234 publications

References 59 publications

Ligand‐Controlled Regiodivergent Hydroalkylation of Pyrrolines

Ligand‐Controlled Regiodivergent Hydroalkylation of Pyrrolines

Recent Developments in C–C Bond Formation Using Catalytic Reductive Coupling Strategies

Recent Advances in Radical Addition to Alkenylboron Compounds

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