Cu/Pd-catalyzed arylboration of a 1-silyl-1,3-cyclohexadiene for stereocontrolled and diverse cyclohexane/ene synthesis

Crook, Phillip F.; Lear, Alan R.; Das, Suman; Brown, M. Kevin

doi:10.1039/d3sc02536e

Chem. Sci.

2023

DOI: 10.1039/d3sc02536e

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Cu/Pd-catalyzed arylboration of a 1-silyl-1,3-cyclohexadiene for stereocontrolled and diverse cyclohexane/ene synthesis

Phillip F. Crook,

Alan R. Lear,

Suman Das

et al.

Abstract: Versatile diene allows for the synthesis of diverse cyclohexane/ene by a Cu/Pd-catalyzed arylboration.

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2024

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Cited by 3 publications

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Enantioselective Borylative Functionalization of Internal Alkenes: A Platform for Constructing Vicinal Stereocenters^†

Zhu,

Li,

Zhao

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryVicinal stereogenic centers are ubiquitous structural scaffolds in both natural products and synthetic compounds, yet their enantioselective construction remains a significant challenge in organic synthesis. Organoboron compounds are of paramount importance in synthetic chemistry due to their ability to undergo facile transformations, yielding diverse essential chemical bonds such as carbon‐carbon, carbon‐oxygen, carbon‐nitrogen, and carbon‐halogen bonds. Transition‐metal‐catalyzed asymmetric borylative functionalizations of internal alkenes offer a promising strategy for the enantioselective installation of two adjacent chiral centers across carbon‐carbon bonds. By leveraging the versatile transformations of the newly introduced boryl unit, this approach holds great potential for expanding the structural diversity of vicinal stereogenic scaffolds. In this concise review, we aim to highlight recent advancements in transition‐metal‐catalyzed asymmetric borylative functionalizations of internal alkenes, underscore their utility as a versatile approach for constructing vicinal stereogenic centers, and discuss unsolved challenges and future directions in this field. Key Scientists

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Enantioselective Borylative Functionalization of Internal Alkenes: A Platform for Constructing Vicinal Stereocenters^†

Zhu,

Li,

Zhao

et al. 2024

Chin. J. Chem.

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Coordination-Assisted Ni-Catalyzed Regio- and Enantioselective 1,2-Borylalkylation of Unactivated Alkenes

Zhu,

Feng,

et al. 2024

Org. Lett.

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Chiral N-Hydroxyalkyl Pyrid-2-Ylidenes: A New Class of Ligands for Copper-Catalyzed Asymmetric Allylic Alkylation

Bouëtard,

Zhang,

Vives

et al. 2024

ACS Catal.

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A class of chiral N-heterocyclic carbenes derived from pyridine, namely N-hydroxyalkyl pyrid-2-ylidenes, was developed. Capitalizing the remarkable steric and electronic features of the pyrid-2-ylidene core with the presence of a chiral hydroxyalkyl-chelating arm on the nitrogen atom, these ligands demonstrated high performance in copper-catalyzed asymmetric allylic alkylation of dialkylzincs to various allylic or dienic phosphates with high γ-selectivity (>98%) and enantioselectivity (up to 95% ee). Importantly, the catalyst loading can be decreased to below 0.5 mol% without any loss of catalyst efficiency, thus outperforming N-hydroxyalkyl imidazoline-2-ylidene congeners. Moreover, thanks to the versatile post-transformation of the resulting enantioenriched skipped 1,4-dienes, various relevant building blocks were synthesized, notably a key intermediate in the total synthesis of (+)-Phorbasin C. Furthermore, by involving a transient oxazolidine, which acts as a masked carbene before the insertion of the metal center, a well-defined but air-sensitive N-hydroxyalkyl pyrid-2-ylidene copper(I) chloride complex was isolated. Deuteration experiments and computational studies provided valuable insights into the formation of the oxazolidine and the corresponding copper complex.

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Cu/Pd-catalyzed arylboration of a 1-silyl-1,3-cyclohexadiene for stereocontrolled and diverse cyclohexane/ene synthesis

Abstract: Versatile diene allows for the synthesis of diverse cyclohexane/ene by a Cu/Pd-catalyzed arylboration.

Cited by 3 publications

References 49 publications

Enantioselective Borylative Functionalization of Internal Alkenes: A Platform for Constructing Vicinal Stereocenters^†

Enantioselective Borylative Functionalization of Internal Alkenes: A Platform for Constructing Vicinal Stereocenters^†

Coordination-Assisted Ni-Catalyzed Regio- and Enantioselective 1,2-Borylalkylation of Unactivated Alkenes

Chiral N-Hydroxyalkyl Pyrid-2-Ylidenes: A New Class of Ligands for Copper-Catalyzed Asymmetric Allylic Alkylation

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Cu/Pd-catalyzed arylboration of a 1-silyl-1,3-cyclohexadiene for stereocontrolled and diverse cyclohexane/ene synthesis

Abstract: Versatile diene allows for the synthesis of diverse cyclohexane/ene by a Cu/Pd-catalyzed arylboration.

Cited by 3 publications

References 49 publications

Enantioselective Borylative Functionalization of Internal Alkenes: A Platform for Constructing Vicinal Stereocenters†

Enantioselective Borylative Functionalization of Internal Alkenes: A Platform for Constructing Vicinal Stereocenters†

Coordination-Assisted Ni-Catalyzed Regio- and Enantioselective 1,2-Borylalkylation of Unactivated Alkenes

Chiral N-Hydroxyalkyl Pyrid-2-Ylidenes: A New Class of Ligands for Copper-Catalyzed Asymmetric Allylic Alkylation

Contact Info

Product

Resources

About

Enantioselective Borylative Functionalization of Internal Alkenes: A Platform for Constructing Vicinal Stereocenters^†

Enantioselective Borylative Functionalization of Internal Alkenes: A Platform for Constructing Vicinal Stereocenters^†