Cobalt-Catalyzed Desymmetric Isomerization of Exocyclic Olefins

Liu, Xufang; Rong, Xianle; Liu, Shihan; Lan, Yu; Liu, Qiang

doi:10.1021/jacs.1c11343

Cited by 39 publications

(21 citation statements)

References 80 publications

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“…The crude residue was then purified by silica flash column chromatography to yield the desired alkene precursor. The literature data for compounds 2m , 2n , 2o , 2p , 2q , 2r , 2t , 2u , 2x , and 2z matched the data obtained using this procedure.…”

Section: Methodssupporting

confidence: 73%

Multicomponent Direct Assembly of N-Heterospirocycles Facilitated by Visible-Light-Driven Photocatalysis

Griffiths

Ley

2022

J. Org. Chem.

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N -heterospirocycles are interesting structural units found in both natural products and medicinal compounds but have relatively few reliable methods for their synthesis. Here, we enlist the photocatalytic generation of N -centered radicals to construct β-spirocyclic pyrrolidines from N -allylsulfonamides and alkenes. A variety of β-spirocyclic pyrrolidines have been constructed, including drug derivatives, in moderate to very good yields. Further derivatization of the products has also been demonstrated as has a viable scale-up procedure, making use of flow chemistry techniques.

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Section: Methodssupporting

confidence: 73%

Multicomponent Direct Assembly of N-Heterospirocycles Facilitated by Visible-Light-Driven Photocatalysis

Griffiths

Ley

2022

J. Org. Chem.

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“…3 Alternatively, transposition of pre-existing olefins offers a powerful and atom-economical route to incorporate and manipulate C=C bonds with far-reaching applications in industrial production, e.g., pharmaceuticals, cosmetics, fragrances, polymers, and fuels. 1b , 4 Various processes were developed with efficient catalysts based on transition metals: Ir, 5 Rh, 6 Pd, 7 Ru, 8 Cr, 9 Co, 10 Ni, 11 Fe, 12 and W, 13 among others ( Figure 1 a). Missing in this set of examples is the highly abundant and biocompatible manganese metal that remains unknown in olefin transposition so far.…”

mentioning

confidence: 99%

Switching between Hydrogenation and Olefin Transposition Catalysis via Silencing NH Cooperativity in Mn(I) Pincer Complexes

et al. 2022

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While Mn-catalyzed (de)hydrogenation of carbonyl derivatives has been well established, the reactivity of Mn hydrides with olefins remains very rare. Herein, we report a Mn(I) pincer complex that effectively promotes site-controlled transposition of olefins. This reactivity is shown to emerge once the N–H functionality within the Mn/NH bifunctional complex is suppressed by alkylation. While detrimental for carbonyl (de)hydrogenation, such masking of the cooperative N–H functionality allows for the highly efficient conversion of a wide range of allylarenes to higher-value 1-propenybenzenes in near-quantitative yield with excellent stereoselectivities. The reactivity toward a single positional isomerization was also retained for long-chain alkenes, resulting in the highly regioselective formation of 2-alkenes, which are less thermodynamically stable compared to other possible isomerization products. The detailed mechanistic analysis of the reaction between the activated Mn catalyst and olefins points to catalysis operating via a metal–alkyl mechanism—one of the three conventional transposition mechanisms previously unknown in Mn complexes.

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“…In 2021, Liu developed a desymmetric isomerization strategy to synthesize chiral cyclohexene derivatives from exocyclic olefins [ 117 ] ( Scheme 10 b). They designed and prepared a set of chiral NNP-pincer cobalt catalysts for this transformation and employed it for the asymmetric synthesis of β -bisabolene, a fragrant sesquiterpene found in many essential oils that has antitumor activity.…”

Section: Synthesis Of Fragrances Via Rearrangement or Isomerizationmentioning

confidence: 99%

Synthesis of Cyclic Fragrances via Transformations of Alkenes, Alkynes and Enynes: Strategies and Recent Progress

Lin¹,

Huang²,

Ouyang³

et al. 2022

Molecules

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With increasing demand for customized commodities and the greater insight and understanding of olfaction, the synthesis of fragrances with diverse structures and odor characters has become a core task. Recent progress in organic synthesis and catalysis enables the rapid construction of carbocycles and heterocycles from readily available unsaturated molecular building blocks, with increased selectivity, atom economy, sustainability and product diversity. In this review, synthetic methods for creating cyclic fragrances, including both natural and synthetic ones, will be discussed, with a focus on the key transformations of alkenes, alkynes, dienes and enynes. Several strategies will be discussed, including cycloaddition, catalytic cyclization, ring-closing metathesis, intramolecular addition, and rearrangement reactions. Representative examples and the featured olfactory investigations will be highlighted, along with some perspectives on future developments in this area.

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Cobalt-Catalyzed Desymmetric Isomerization of Exocyclic Olefins

Cited by 39 publications

References 80 publications

Multicomponent Direct Assembly of N-Heterospirocycles Facilitated by Visible-Light-Driven Photocatalysis

Multicomponent Direct Assembly of N-Heterospirocycles Facilitated by Visible-Light-Driven Photocatalysis

Switching between Hydrogenation and Olefin Transposition Catalysis via Silencing NH Cooperativity in Mn(I) Pincer Complexes

Synthesis of Cyclic Fragrances via Transformations of Alkenes, Alkynes and Enynes: Strategies and Recent Progress

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