Nickel-Catalyzed, Stereospecific C–C and C–B Cross-Couplings via C–N and C–O Bond Activation

Xu, Jianyu; Bercher, Olivia P.; Talley, Michael R.; Watson, Mary P.

doi:10.1021/acscatal.0c05484

Cited by 56 publications

(17 citation statements)

References 54 publications

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“…Transition-metal-catalyzed C–O bond activation provides a valuable approach to the synthetic application of alcohol and phenol derivatives. − Through the meticulous design of nickel catalysis, a wide array of cross-coupling reactions were developed for phenol-derived electrophiles, which enabled a divergent set of transformations of the strong C(aryl)–O bond (Scheme a). − On the basis of Ni-catalyzed C(sp 3 )–O bond activation, the development of stereospecific cross-coupling reactions opened new reaction channels for the stereoselective transformations of benzylic and allylic alcohol derivatives (Scheme b). − Both retentive and invertive transformations were realized through the judicious selection of ligand, solvent, and substrate. , In contrast to the nickel catalysis, the palladium-catalyzed C(sp 2 )–O bond activation presented exclusive selectivity toward the C(acyl)–O bond cleavage, which stimulated the advancement of cross-couplings involving aryl carboxylic acid derivatives (Scheme c) . Depending on the chemoselectivity control between decarbonylation ,− and carbonyl retention, novel pathways for the palladium-catalyzed synthesis of acyl and aryl compounds were designed.…”

Section: Introductionmentioning

confidence: 99%

Mechanism and Selectivity Control in Ni- and Pd-Catalyzed Cross-Couplings Involving Carbon–Oxygen Bond Activation

Zhang

Hong

2021

Acc. Chem. Res.

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Conspectus Transition-metal-catalyzed C–O bond activation provides a useful strategy for utilizing alcohol- and phenol-derived electrophiles in cross-coupling reactions, which has become a research field of active and growing interest in organic chemistry. The synergy between computation and experiment elucidated the mechanistic model and controlling factors of selectivities in these transformations, leading to advances in innovative C–O bond activation and functionalization methods. Toward the rational design of C–O bond activation, our collaborations with the Jarvo group bridged the mechanistic models of C(sp2)–O and C(sp3)–O bond activations. We found that the nickel catalyst cleaves the benzylic and allylic C(sp3)–O bonds via two general mechanisms: the stereoinvertive SN2 back-side attack model and the stereoretentive chelation-assisted model. These two models control the stereochemistry in a wide array of stereospecific Ni-catalyzed cross-coupling reactions with benzylic or allylic alcohol derivatives. Because of the catalyst distortion, the ligands can differentiate the competing stereospecific C(sp3)–O bond activations. The PCy3 ligand interacts with nickel mainly through σ-donation, and the Ni(PCy3) catalyst can undergo facile bending of the substrate–nickel–ligand angle, which favors the stereoretentive benzylic C–O bond activation. The N-heterocyclic carbene SIMes ligand has additional d(metal)–p(ligand) back-donation with nickel, which leads to an extra energy penalty for the same angle bending. This results in the preference of stereoinvertive benzylic C–O bond activation under Ni/SIMes catalysis. In addition to ligand control, a Lewis acid can increase the selectivity for stereoinvertive C(sp3)–O activation by stabilizing the SN2 back-side attack transition state. The oxygen leaving group complexes with the MgI2 Lewis acid in the stereoinvertive activation, leading to the exclusive stereoinvertive Kumada coupling of benzylic ethers. We also identified that the competing C(sp3)–O bond activation models have noticeable differences in charge separation. This leads to the solvent polarity control of the stereospecificity in C(sp3)–O activations. Low-polarity solvents favor the neutral stereoretentive C–O bond activation, while high-polarity solvents favor the zwitterionic stereoinvertive cleavage. In sharp contrast to the nickel catalysts, the C(sp2)–O bond activation under palladium catalysis mainly proceeds via the classic three-membered ring oxidative addition mechanism instead of the chelation-assisted mechanism. This is due to the lower oxophilicity of palladium, which disfavors the oxygen coordination in the chelation-assisted-type activation. The three-membered ring activation model selectively cleaves the weak C–O bond, resulting in the exclusive chemoselectivity of acyl C–O bond activation in Pd-catalyzed cross-coupling reactions with aryl carboxylic acid derivatives. This explains the overall acylation in the Pd-catalyzed Suzuki–Miyaura coupling with aryl esters. In collaboration wi...

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Section: Introductionmentioning

confidence: 99%

Mechanism and Selectivity Control in Ni- and Pd-Catalyzed Cross-Couplings Involving Carbon–Oxygen Bond Activation

Zhang

Hong

2021

Acc. Chem. Res.

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“…Asymmetric allylic substitution reactions have been the subject of intense study, finding broad applications in the synthesis of natural products . In this context, the enantiospecific reactions harness the ease of preparation of highly enantioenriched secondary allylic alcohols and avoid the requirement for chiral ligands . Moreover, they provide access to acyclic products with internal alkenes, which are always difficult to produce by enantioconvergent methods.…”

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confidence: 99%

Cobalt-Catalyzed Enantiospecific Dynamic Kinetic Cross-Electrophile Vinylation of Allylic Alcohols with Vinyl Triflates

Han

Kang

et al. 2021

J. Am. Chem. Soc.

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Asymmetric cross-electrophile coupling has emerged as a promising tool for producing chiral molecules; however, the potential of this chemistry with metals other than nickel remains unknown. Herein, we report a cobalt-catalyzed enantiospecific vinylation reaction of allylic alcohol with vinyl triflates. This work establishes a new method for the synthesis of enantioenriched 1,4-dienes. The reaction proceeds through a dynamic kinetic coupling approach, which not only allows for direct functionalization of allylic alcohols but also is essential to achieve high chemoselectivity. The use of cobalt enables the reactions to proceed with high enantiospecificity, which have failed to be realized by nickel catalysts.

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“…In addition, these moieties are appealing because they are common functional groups in synthesis. Furthermore, we demonstrate that sulfonamides undergo stereospecific XC reactions, in contrast to the stereoablative reactivity typically observed with styrenyl aziridines and Katritzky salts [ 22 , 36 , 37 , 38 , 39 , 40 , 51 , 52 , 53 , 54 ]. This stereospecific manifold allows for rapid diastereoselective construction of acyclic fragments bearing 1,3-substitution [ 55 , 56 ].…”

Section: Introductionmentioning

confidence: 80%

Nickel-Catalyzed Kumada Cross-Coupling Reactions of Benzylic Sulfonamides

et al. 2021

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Nickel-Catalyzed, Stereospecific C–C and C–B Cross-Couplings via C–N and C–O Bond Activation

Cited by 56 publications

References 54 publications

Mechanism and Selectivity Control in Ni- and Pd-Catalyzed Cross-Couplings Involving Carbon–Oxygen Bond Activation

Mechanism and Selectivity Control in Ni- and Pd-Catalyzed Cross-Couplings Involving Carbon–Oxygen Bond Activation

Cobalt-Catalyzed Enantiospecific Dynamic Kinetic Cross-Electrophile Vinylation of Allylic Alcohols with Vinyl Triflates

Nickel-Catalyzed Kumada Cross-Coupling Reactions of Benzylic Sulfonamides

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