Rh2(R-TPCP)4-Catalyzed Enantioselective [3+2]-Cycloaddition between Nitrones and Vinyldiazoacetates

Qin, Changming; Davies, Huw M. L.

doi:10.1021/ja4069003

Cited by 98 publications

(69 citation statements)

References 33 publications

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“…A related analogue, Rh 2 ( R -TPCP) 4 was employed for the generation of [3+2] cycloaddition products derived from initial attack at the vinylogous position of the rhodium vinylcarbene. 24 Most recently, the biphenyl derivative Rh 2 ( R -BPCP) 4 has shown promise for site selective C–H functionalization. It was applied to the selective functionalization of activated primary C–H bonds, such as allylic and benzylic sites.…”

Section: Introduction1mentioning

confidence: 99%

Enantioselective dirhodium(II)-catalyzed cyclopropanations with trimethylsilylethyl and trichloroethyl aryldiazoacetates

et al. 2015

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Highly functionalized cyclopropanecarboxylates were readily prepared by rhodium-catalyzed cyclopropanation of alkenes with aryldiazoacetates and styryldiazoaceates, in which the ester functionality is either trimethylsilylethyl (TMSE) or trichlorethyl (TCE). By having labile protecting groups on the ester, chiral triarylcyclopropane carboxylate ligands were conveniently prepared. The asymmetric induction during cyclopropanation is dependent on the nature of the ester group and the chiral dirhodium tetracarboxylate catalyst. The prolinate catalyst Rh2(S-DOSP)4 was the optimum catalyst for asymmetric intermolecular cyclopropanation of TMSE diazoesters with styrene, while Rh2(R-BPCP)4 was the optimum catalyst for TCE diazoesters.

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Section: Introduction1mentioning

confidence: 99%

Enantioselective dirhodium(II)-catalyzed cyclopropanations with trimethylsilylethyl and trichloroethyl aryldiazoacetates

et al. 2015

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“…In the same context, Rh2(R-BTPCP)4 was also reported as a catalyst that exhibited high enantioselectivity levels [73][74][75]. For example, the Rh2(R-BTPCP)4-catalyzed cyclopropanation of styrene with methyl styryldiazoacetate generated the cyclopropane product in 92% ee [73].…”

Section: Ligand Blocking Groups Arrangementsmentioning

confidence: 95%

On the Structure of Chiral Dirhodium(II) Carboxylate Catalysts: Stereoselectivity Relevance and Insights

Adly

2017

Catalysts

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Abstract:Modern experiments have offered alternative interpretations on the symmetry of chiral dirhodium(II) carboxylate complexes and its relationship to their level of enantioselectivity. So, this contribution is to provide an insight on how the knowledge around the structure of these catalysts has evolved with a particular emphasis on the impact of this knowledge on enantioselectivity prediction and catalyst design.

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“…In contrast, [2+3]-cycloaddition products were obtained from dirhodium(II)-catalyzed reactions between β-unsubstituted vinyldiazoacetates and nitrones, in which the metallo-vinylcarbenes participated only as two-carbon components (the carbon–carbon double bond). 119 This comparison indicates that the β-silyloxy substituents of enoldiazo compounds play a crucial role in enhancing the [3+3]-cycloaddition process 118 and in inhibiting other competing reaction pathways. 119–121 …”

Section: Mecc Reactions Of Enoldiazo Compoundsmentioning

confidence: 99%

Cycloaddition reactions of enoldiazo compounds

et al. 2017

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Enoldiazo esters and amides have proven to be versatile reagents for cycloaddition reactions that allow highly efficient construction of various carbocycles and heterocycles. Their versatility is exemplified by (1) [2+n]-cycloadditions (n = 3, 4) by the enol silyl ether units of enoldiazo compounds with retention of the diazo functionality to furnish α-cyclic-α-diazo compounds that are themselves subject to further transformations of the diazo functional group; (2) [3+n]-cycloadditions (n = 1–5) by metallo-enolcarbenes formed by catalytic dinitrogen extrusion from enoldiazo compounds; (3) [2+n]-cycloadditions (n = 3, 4) by donor–acceptor cyclopropenes generated in situ from enoldiazo compounds that produce cyclopropane-fused ring systems. The role of dirhodium(II) and the emergence of copper(I) catalysts are described, as are the different outcomes of reactions initiated with these catalysts. This comprehensive review on cycloaddition reactions of enoldiazo compounds, with emphasis on methodology development, mechanistic insight, and catalyst-controlled chemodivergence, aims to provide inspiration for future discoveries in the field and to catalyze the application of enoldiazo reagents by the wider synthetic community.

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Rh₂(R-TPCP)₄-Catalyzed Enantioselective [3+2]-Cycloaddition between Nitrones and Vinyldiazoacetates

Cited by 98 publications

References 33 publications

Enantioselective dirhodium(II)-catalyzed cyclopropanations with trimethylsilylethyl and trichloroethyl aryldiazoacetates

Enantioselective dirhodium(II)-catalyzed cyclopropanations with trimethylsilylethyl and trichloroethyl aryldiazoacetates

On the Structure of Chiral Dirhodium(II) Carboxylate Catalysts: Stereoselectivity Relevance and Insights

Cycloaddition reactions of enoldiazo compounds

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