Asymmetric Alkenylation of Enones and Imines Enabled by A Highly Efficient Aryl to Vinyl 1,4‐Rhodium Migration

Zhang, Shusheng; Hu, Tianjiao; Li, Mengyao; Song, Yi-Kang; Yang, Xiaodi; Feng, Chen‐Guo; Lin, Guo‐Qiang

doi:10.1002/anie.201813585

Cited by 50 publications

(16 citation statements)

References 69 publications

(13 reference statements)

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“…Thea bsolute configuration of 7c was unambiguously determined to be R by X-ray crystallography (Figure 1), [20] which is in accordance to the stereochemistry-defining model for the arylation of cyclohexenone previously proposed by the Hayashi group. [21] Theconfigurations of other cyclohexenone adducts were also assigned as R by assuming asimilar reaction pathway.…”

supporting

confidence: 82%

Asymmetric Alkenylation of Enones and Imines Enabled by A Highly Efficient Aryl to Vinyl 1,4‐Rhodium Migration

Zhang

et al. 2019

Angewandte Chemie

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The asymmetric rhodium-catalyzed alkenylation of enones and imines with arylboronic acids has been developed. Ahighly controllable aryl to vinyl 1,4-rhodium migration is the key step.S tereodefined vinyl moieties were installed in excellent enantioselectivies for most examined examples. DFT calculations reveal that the driving force of this rhodium migration is akinetically favored process. Scheme 1. New reactivity of organoboronates enabled by 1,4-rhodium migration.Scheme 2. Proposed strategy.[*] Dr.

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supporting

confidence: 82%

Asymmetric Alkenylation of Enones and Imines Enabled by A Highly Efficient Aryl to Vinyl 1,4‐Rhodium Migration

Zhang

et al. 2019

Angewandte Chemie

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“…Since the first example on Rh-catalyzed addition of boronic acids to alkynes, several methods relying on the ability of alkenyl-rhodium species to promote an intramolecular 1,4-migration to the corresponding aryl-rhodium intermediate have been disclosed . This 1,4-shift offers the opportunity to employ arylboron reagents with a free C–H bond at the ortho position as 1,2-dimetallate synthons (Scheme ).…”

Section: Hydroarylation/cyclization Via Dyotropic Rearrangementsmentioning

confidence: 99%

Transition-Metal-Catalyzed Functionalization of Alkynes with Organoboron Reagents: New Trends, Mechanistic Insights, and Applications

et al. 2021

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Catalytic functionalization of alkynes with organoboron reagents provides a straightforward access to stereochemically defined multisubstituted alkenes, which are structural motifs commonly found in bioactive compounds and organic materials. Recent progress has substantially broadened the scope of this field on several fronts. Strategies for regioselectivity control in the 1,2-migratory insertion across unsymmetrical internal alkynes, as well as for the direct access to products with anti-insertion stereochemistry, have been devised. The alkenyl-to-aryl 1,4-metal migration upon metal insertion has been recently exploited in powerful cascade sequences leading to complex polycyclic scaffolds, including the development of enantioselective processes. Elegant enantiospecific and dynamic kinetic resolution methods have been developed for accessing chiral allenes from propargylic alcohol derivatives. Mechanistic manifolds have emerged based on single-electron transfer (SET) that have provided a fresh impetus for alkyne 1,2-difunctionalization with complementary stereoselectivity to processes relying on 1,2-insertion of R–M species. Herein, we discuss the most recent advances in transition-metal-catalyzed functionalization of alkynes using organoboron reagents, categorized according to the type of mechanistic outcome. Emphasis is placed on mechanistic aspects, synthetic utility, limitations, and challenges for future research.

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“…Notably, no waste is generated since both phenolic dienes 8 and 9 could be functionalized in a second run, while the diphenyldiene L3 serves perfectly as a benchmark ligand with broad applications. [72][73][74][75][76][77] Williamson etherification of 8 with 1.1 equiv. 6-chloro-1-hexyne in the presence of Cs 2 CO 3 in DMSO gave the mono-functionalized alkyne L1 in a yield of 53 %.…”

Section: Molecular Heterogeneous Catalysis With Sio 2 à Io Solid Supportmentioning

confidence: 99%

Hierarchical Silica Inverse Opals as a Catalyst Support for Asymmetric Molecular Heterogeneous Catalysis with Chiral Rh‐diene Complexes

et al. 2021

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The efficacy of heterogeneous catalysis relies heavily on diffusion and distribution of reactants within catalyst supports. However, the presence of confinement, essential for reaction selectivity, drastically slows down molecular transport. Here, macro-mesoporous silica inverse opal (SiO 2 À IO) films were used as a model system to study the rather unexplored molecular infiltration behavior using a probe molecule resembling a catalyst via confocal laser scanning microscopy (CLSM). CLSM analysis revealed homogeneous tracer distribution in SiO 2 À IO and attachment to both transport and mesopores. Bulk macro-mesoporous SiO 2 À IO support was used for the attachment of mono-and bis-functionalized chiral Rh-diene complexes, and the catalytic activity and selectivity with respect to the support was studied. Lower enantioselectivity was observed with the bis-functionalized ligand due to ligand entanglement and reduced accessibility of the active site, while the monofunctionalized ligand gave an excellent enantioselectivity of 94 %ee in the asymmetric 1,2-addition of triphenylboroxine to N-tosylimines and could be recycled up to three times.

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Asymmetric Alkenylation of Enones and Imines Enabled by A Highly Efficient Aryl to Vinyl 1,4‐Rhodium Migration

Cited by 50 publications

References 69 publications

Asymmetric Alkenylation of Enones and Imines Enabled by A Highly Efficient Aryl to Vinyl 1,4‐Rhodium Migration

Asymmetric Alkenylation of Enones and Imines Enabled by A Highly Efficient Aryl to Vinyl 1,4‐Rhodium Migration

Transition-Metal-Catalyzed Functionalization of Alkynes with Organoboron Reagents: New Trends, Mechanistic Insights, and Applications

Hierarchical Silica Inverse Opals as a Catalyst Support for Asymmetric Molecular Heterogeneous Catalysis with Chiral Rh‐diene Complexes

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