A Nickel-Catalyzed Cross-Electrophile Coupling Reaction of 1,3-Dimesylates for Alkylcyclopropane Synthesis: Investigation of Stereochemical Outcomes and Radical Lifetimes

Chen, Pan‐Pan; McGinnis, Tristan M.; Lin, Patricia C.; Hong, Xin; Jarvo, Elizabeth R.

doi:10.1021/acscatal.3c00905

Cited by 7 publications

(7 citation statements)

References 74 publications

(43 reference statements)

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“…A number of experiments were performed to determine the key features of the mechanism of the XEC reaction (Scheme 4). First, we looked to confirm that the alkyl iodides resulting from displacement of the sulfonate starting materials were intermediates in the reaction [6a,c,9d,10a,13a,14a,b,17] . A reaction with iodomethane rather than methyl tosylate resulted in 41 % yield of the methylated product (Scheme 4a).…”

Section: Resultsmentioning

confidence: 99%

Cross‐selective Deoxygenative Coupling of Aliphatic Alcohols: Installation of Methyl Groups including Isotopic Labels by Nickel Catalysis

Lin,

Wong,

Jarvo

2024

Angew Chem Int Ed

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Nickel‐catalyzed cross‐electrophile coupling reactions of two aliphatic alcohol derivatives remain a challenge. Herein, we report a nickel‐catalyzed reductive methylation reaction of aliphatic mesylates with methyl tosylate. This reaction provides straightforward access to compounds bearing aliphatic methyl groups from alkyl alcohol derivatives. Isotopically labelled substrates and reagents can be employed in the reaction to provide perdeuterated and 13C‐labelled products. This transformation can be achieved by employing stoichiometric Mn reductant or electrochemically. Additionally, mechanistic experiments show that alkyl iodides are key intermediates in the transformation which undergo a stereoablative reaction via radical intermediates.

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Section: Resultsmentioning

confidence: 99%

Cross‐selective Deoxygenative Coupling of Aliphatic Alcohols: Installation of Methyl Groups including Isotopic Labels by Nickel Catalysis

Lin,

Wong,

Jarvo

2024

Angew Chem Int Ed

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“…In BSII, the 6-311+G(d,p) basis set was employed for the nonmetallic atoms, and the SDD basis set was adopted for the Sc and Y atoms. To reduce the overestimation of the entropy contribution derived from the gas-phase model, a correction of −4.3 kcal/mol in free energy was applied for each two-to-one molecule transformation . Distortion–interaction analysis was performed on key TSs with M06/BSII level.…”

Section: Computational Detailsmentioning

confidence: 99%

Unveiling the Detailed Mechanism and Origins of Chemo-, Regio-, and Stereoselectivity of Rare-Earth Catalyzed Alternating Copolymerization of Polar and Nonpolar Olefins

Zhang,

Xue,

Shi

et al. 2024

Inorg. Chem.

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The direct copolymerization of polar and nonpolar olefins is of great interest and significance, as it is the most atomeconomical and straightforward strategy for the synthesis of functional polyolefin materials. Despite considerable efforts, the precise control of monomer-sequence and their regio-and stereochemistry is full of challenges, and the related mechanistic origins are still in their infancy to date. Herein, the mechanistic studies on the model reaction of Sc-catalyzed co-syndiospecific alternating copolymerization of anisylpropylene (AP) and styrene were performed by DFT calculations. The results suggest that the subtle balance between electronic and steric factors plays an important role during monomer insertions, and a new aminodissociated mechanism was proposed for AP insertion at chain initiation. AP insertion follows the 2,1-si-insertion pattern, which is mainly controlled by steric factors caused by the restricted MeO•••Sc interaction. As for styrene insertion, it prefers the 2,1-reinsertion manner and its regio-and stereoselectivities are influenced by steric repulsions between the inserting styrene and the polymer chain or the ligand. More interestingly, it is found that the alternating monomer-sequence is mainly determined by the "steric matching" principle, which is quantitatively expressed by the buried volume of the metal center of the preinserted species. The concept of steric pocket has been successfully applied to explain the different performances of several catalysts and other alternating copolymerization reactions. The insightful mechanistic findings and the quantitative steric pocket model present here are expected to promote rational design of new rare-earth catalysts for developing regio-, stereo-, and sequence-controlled copolymerization of specific polar and nonpolar olefins.

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“…Despite significant progress in the selective construction of carbon–carbon bonds, developing regio- and stereoselective catalytic methods for C(sp 3 )–C(sp 3 ) coupling that generate vicinal stereocenters continues to be a major challenge in synthetic organic chemistry. Strategies such as transition-metal-catalyzed alkyl–alkyl cross-coupling between alkyl electrophiles and alkyl nucleophiles, − as well as reductive cross-electrophile coupling, − have evolved rapidly in recent decades. However, there is a need for advancing toward enantioconvergent and highly enantio- and diastereoselective processes that avoid stoichiometric alkyl metal/metalloid reagents or metal reductants.…”

Section: Introductionmentioning

confidence: 99%

Interception of Transient Allyl Radicals with Low-Valent Allylpalladium Chemistry: Tandem Pd(0/II/I)–Pd(0/II/I/II) Cycles in Photoredox/Pd Dual-Catalytic Enantioselective C(sp³)–C(sp³) Homocoupling

Li,

Zhang,

Luo

et al. 2024

J. Am. Chem. Soc.

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We present comprehensive computational and experimental studies on the mechanism of an asymmetric photoredox/Pd dual-catalytic reductive C(sp 3 )−C(sp 3 ) homocoupling of allylic electrophiles. In stark contrast to the canonical assumption that photoredox promotes bond formation via facile reductive elimination from high-valent metal−organic species, our computational analysis revealed an intriguing low-valent allylpalladium pathway that features tandem operation of Pd(0/II/I)−Pd(0/II/I/II) cycles. Specifically, we propose that (i) the photoredox/Pd system enables the in situ generation of allyl radicals from low-valent Pd(I)-allyl species, and (ii) effective interception of the fleeting allyl radical by the chiral Pd(I)-allyl species results in the formation of an enantioenriched product. Notably, the cooperation of the two pathways highlights the bifunctional role of Pd(I)allyl species in the generation and interception of transient allyl radicals. Moreover, the mechanism implies divergent substrateactivation modes in this homocoupling reaction, suggesting a theoretical possibility for cross-coupling. Combined, the current study offers a novel mechanistic hypothesis for photoredox/Pd dual catalysis and highlights the use of low-valent allylpalladium as a means to efficiently intercept radicals for selective asymmetric bond constructions.

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A Nickel-Catalyzed Cross-Electrophile Coupling Reaction of 1,3-Dimesylates for Alkylcyclopropane Synthesis: Investigation of Stereochemical Outcomes and Radical Lifetimes

Cited by 7 publications

References 74 publications

Cross‐selective Deoxygenative Coupling of Aliphatic Alcohols: Installation of Methyl Groups including Isotopic Labels by Nickel Catalysis

Cross‐selective Deoxygenative Coupling of Aliphatic Alcohols: Installation of Methyl Groups including Isotopic Labels by Nickel Catalysis

Unveiling the Detailed Mechanism and Origins of Chemo-, Regio-, and Stereoselectivity of Rare-Earth Catalyzed Alternating Copolymerization of Polar and Nonpolar Olefins

Interception of Transient Allyl Radicals with Low-Valent Allylpalladium Chemistry: Tandem Pd(0/II/I)–Pd(0/II/I/II) Cycles in Photoredox/Pd Dual-Catalytic Enantioselective C(sp³)–C(sp³) Homocoupling

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A Nickel-Catalyzed Cross-Electrophile Coupling Reaction of 1,3-Dimesylates for Alkylcyclopropane Synthesis: Investigation of Stereochemical Outcomes and Radical Lifetimes

Cited by 7 publications

References 74 publications

Cross‐selective Deoxygenative Coupling of Aliphatic Alcohols: Installation of Methyl Groups including Isotopic Labels by Nickel Catalysis

Cross‐selective Deoxygenative Coupling of Aliphatic Alcohols: Installation of Methyl Groups including Isotopic Labels by Nickel Catalysis

Unveiling the Detailed Mechanism and Origins of Chemo-, Regio-, and Stereoselectivity of Rare-Earth Catalyzed Alternating Copolymerization of Polar and Nonpolar Olefins

Interception of Transient Allyl Radicals with Low-Valent Allylpalladium Chemistry: Tandem Pd(0/II/I)–Pd(0/II/I/II) Cycles in Photoredox/Pd Dual-Catalytic Enantioselective C(sp3)–C(sp3) Homocoupling

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Interception of Transient Allyl Radicals with Low-Valent Allylpalladium Chemistry: Tandem Pd(0/II/I)–Pd(0/II/I/II) Cycles in Photoredox/Pd Dual-Catalytic Enantioselective C(sp³)–C(sp³) Homocoupling