Asymmetric Rearrangement and Insertion Reactions with Metal–Carbenoids Promoted by Chiral
            <scp>
              <i>N,N</i>
              <i>′</i>
            </scp>
            ‐Dioxide or Guanidine‐Based Catalysts

Lin, Xiaobin; Liu, Xiaohua; Feng, Xiaoming

doi:10.1002/9783527829170.ch10

Transition Metal‐Catalyzed Carbene Transformations 2021

DOI: 10.1002/9783527829170.ch10

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Asymmetric Rearrangement and Insertion Reactions with Metal–Carbenoids Promoted by Chiral N,N ′ ‐Dioxide or Guanidine‐Based Catalysts

Xiaobin Lin¹,

Xiaohua Liu²,

Xiaoming Feng³

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2022

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Cited by 2 publications

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Asymmetric Catalytic (2+1) Cycloaddition of Thioketones to Synthesize Tetrasubstituted Thiiranes

Lin

Sang

et al. 2022

Angewandte Chemie

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Herein, we report the first example of enantioselective (2+1) cycloaddition of thioketones with α‐diazo pyrazoleamides for the direct synthesis of tetrasubstituted thiiranes. In the presence of chiral N,N′‐dioxide/cobalt(ΙΙ) complexes (2–5 mol%), excellent efficiency (up to 99 % yield within 15 mins) and high stereoselectivity (up to >19 : 1 dr and 97 % ee) are available. Elaborations of thiiranes via desulfuration have also been conducted to deliver tetrasubstituted olefins. Density functional theory calculations reveal that the reaction initiates from a doublet state cobalt(ΙΙ) carbenoid, which is followed by a quartet cobalt(ΙΙ)‐bound thiocarbonyl ylide pathway. This work provides a route for the selective construction of tetrasubstituted thiiranes and olefins that are otherwise difficult to access.

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Asymmetric Catalytic (2+1) Cycloaddition of Thioketones to Synthesize Tetrasubstituted Thiiranes

Lin

Sang

et al. 2022

Angewandte Chemie

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View full text Add to dashboard Cite

show abstract

Asymmetric Catalytic (2+1) Cycloaddition of Thioketones to Synthesize Tetrasubstituted Thiiranes

Lin

Sang

et al. 2022

Angew Chem Int Ed

Self Cite

View full text Add to dashboard Cite

Herein, we report the first example of enantioselective (2+1) cycloaddition of thioketones with α-diazo pyrazoleamides for the direct synthesis of tetrasubstituted thiiranes. In the presence of chiral N,N'dioxide/cobalt(ΙΙ) complexes (2-5 mol%), excellent efficiency (up to 99 % yield within 15 mins) and high stereoselectivity (up to > 19 : 1 dr and 97 % ee) are available. Elaborations of thiiranes via desulfuration have also been conducted to deliver tetrasubstituted olefins. Density functional theory calculations reveal that the reaction initiates from a doublet state cobalt(ΙΙ) carbenoid, which is followed by a quartet cobalt(ΙΙ)bound thiocarbonyl ylide pathway. This work provides a route for the selective construction of tetrasubstituted thiiranes and olefins that are otherwise difficult to access.

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Asymmetric Rearrangement and Insertion Reactions with Metal–Carbenoids Promoted by Chiral N,N ′ ‐Dioxide or Guanidine‐Based Catalysts

Cited by 2 publications

References 49 publications

Asymmetric Catalytic (2+1) Cycloaddition of Thioketones to Synthesize Tetrasubstituted Thiiranes

Asymmetric Catalytic (2+1) Cycloaddition of Thioketones to Synthesize Tetrasubstituted Thiiranes

Asymmetric Catalytic (2+1) Cycloaddition of Thioketones to Synthesize Tetrasubstituted Thiiranes

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