Recent progress in cobalt-catalyzed enantioselective hydrogenation and hydroboration reactions of alkenes

Yang, Xiaoxu; Ge, Shaozhong

doi:10.1016/j.cogsc.2021.100542

Cited by 20 publications

(3 citation statements)

References 40 publications

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“…Enantioenriched chiral organoboron compounds are versatile building blocks in asymmetric synthesis because they can readily undergo a series of stereospecific reactions by converting their C–B bonds . Therefore, the development of effective catalytic enantioselective protocols to prepare chiral organoboronate compounds is of great importance and has been highly sought after in the fields of organic synthesis, medicinal chemistry, and material sciences . Among various families of structurally diverse chiral boronates, chiral diboronates with distinct C–B bonds are particularly appealing because their two C–B bonds can be sequentially and selectively converted, thus facilitating the synthesis of structurally intricate enantioenriched chiral compounds .…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Copper-Catalyzed Ring-Opening Diboration of Arylidenecyclopropanes to Access Chiral Skipped 1,4- and 1,3-Diboronates

Zheng,

Tan,

et al. 2024

J. Am. Chem. Soc.

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Two enantioselective approaches to synthesize chiral skipped diboronate compounds have been developed, relying on copper-catalyzed one-pot asymmetric ring-opening diboration of arylidenecyclopropanes. A wide range of arylidenecyclopropanes react smoothly with HBpin in the presence of CuOAc and (R)-DTBM-Segphos, affording chiral 1,4-diboronates with high enantioselectivity (up to 99% ee). Meanwhile, a variety of arylidenecyclopropanes react selectively with HBpin and B 2 pin 2 in the presence of CuOAc and (S,S)-Ph-BPE with the sequential addition of MeOH, providing chiral 1,3-diboronates with high enantioselectivity (up to 98% ee). These enantioenriched 1,3-and 1,4-diboronates can undergo various enantiospecific transformations with minimal loss of their enantiopurity. Mechanistic studies reveal that these two diboration processes start with CuH-catalyzed ring-opening hydroboration of arylidenecyclopropanes to form a mixture of Z/E-homoallyl boronate intermediates, which subsequently undergo enantioselective CuH-catalyzed second hydroboration or Cu-Bpin-catalyzed protoboration to produce chiral 1,4-diboronates or 1,3-diboronates, respectively.

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Section: Introductionmentioning

confidence: 99%

Enantioselective Copper-Catalyzed Ring-Opening Diboration of Arylidenecyclopropanes to Access Chiral Skipped 1,4- and 1,3-Diboronates

Zheng,

Tan,

et al. 2024

J. Am. Chem. Soc.

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“…Enantioenriched organoboronates are versatile reagents for asymmetric synthesis as they can undergo various stereospecific transformations with no or minimum loss of their enantiopurity. 4 The installation of boronate functionality into chiral fluoroalkyl compounds will improve their manipulability and enrich their synthetic utility. 5 Catalytic hydroboration or protoboration of fluoroalkyl-substituted alkenes is one straightforward approach to prepare fluoroalkylated organoboronates.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Cobalt-Catalyzed Hydroboration of Fluoroalkyl-Substituted Alkenes to Access Chiral Fluoroalkylboronates

Tan

2022

J. Am. Chem. Soc.

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Selective defluoroborylation and asymmetric hydroboration reactions of fluoroalkyl-substituted terminal alkenes with pinacolborane (HBpin) have been developed with cobalt catalysts generated from Co(acac) 2 and bisphosphine ligands. A variety of fluoroalkyl-substituted terminal alkenes undergo this enantioselective hydroboration, affording the corresponding chiral alkylboronates containing fluoroalkyl-substituted stereogenic carbon centers with high enantioselectivity (up to 98% ee ). This asymmetric hydroboration provides a versatile foundation for the synthesis of a variety of chiral organofluorine compounds containing fluoroalkyl-substituted stereogenic carbon centers.

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“…In addition to their potential lower cost and increased sustainability, first-row transition metal catalysts may also offer enhanced or complementary functional group tolerance and activity compared to their second-and third-row counterparts. 6,7 Moreover, first-row transition metals may undergo both oneand two-electron redox changes, providing new opportunities in precatalyst design, function, and optimization.…”

mentioning

confidence: 99%

Asymmetric Hydrogenation of Indazole-Containing Enamides Relevant to the Synthesis of Zavegepant Using Neutral and Cationic Cobalt Precatalysts

et al. 2023

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The cobalt-catalyzed asymmetric hydrogenation of indazole-containing enamides relevant to the synthesis of the calcitonin gene-related peptide (CGRP) receptor antagonist, zavegepant (1), approved for the treatment of migraines, is described. Both neutral bis(phosphine)cobalt(II) and cationic bis(phosphine)cobalt(I) complexes served as efficient precatalysts for the enamide hydrogenation reactions, providing excellent yield and enantioselectivities (up to >99.9%) for a range of related substrates, though key reactivity differences were observed. Hydrogenation of indazole-containing enamide, methyl (Z)-2-acetamido-3-(7-methyl-1H-indazol-5-yl)acrylate, was performed on a 20 g scale.

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Recent progress in cobalt-catalyzed enantioselective hydrogenation and hydroboration reactions of alkenes

Cited by 20 publications

References 40 publications

Enantioselective Copper-Catalyzed Ring-Opening Diboration of Arylidenecyclopropanes to Access Chiral Skipped 1,4- and 1,3-Diboronates

Enantioselective Copper-Catalyzed Ring-Opening Diboration of Arylidenecyclopropanes to Access Chiral Skipped 1,4- and 1,3-Diboronates

Enantioselective Cobalt-Catalyzed Hydroboration of Fluoroalkyl-Substituted Alkenes to Access Chiral Fluoroalkylboronates

Asymmetric Hydrogenation of Indazole-Containing Enamides Relevant to the Synthesis of Zavegepant Using Neutral and Cationic Cobalt Precatalysts

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