Tandem Rh-catalysis: decarboxylative β-keto acid and alkyne cross-coupling

Cruz, Faben A.; Chen, Zhiwei; Kurtoic, Sarah I.; Dong, Vy M.

doi:10.1039/c6cc02522f

Cited by 92 publications

(19 citation statements)

References 77 publications

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“…In 2016 the Dong group reported an alternative approach to the synthesis of ,-unsaturated ketones from internal alkynes using a -keto acid as the nucleophile by tandem Rh catalysis (Scheme 54). 74 They studied the relationship between ligand bite angle and reactivity and found that the optimal bite angle of approximately 101° (DPEphos, L15) promotes the desired transformation efficiently.…”

Section: Scheme 53 Rh-catalyzed Addition Of 13-dicarbonyl Compounds mentioning

confidence: 99%

Rhodium-Catalyzed Allylation Reactions

Thoke

Kang

2019

Synthesis

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Rhodium-catalyzed allylation reactions are well known for their unique selectivity and reactivity due to the high memory effect of Rh as compared to other metals. These reactions involve the substitution of allylic rhodium intermediates with a diverse range of different nucleophiles, leading to C–C and C–heteroatom bond formation. Modern organic chemists are, however, interested in atom-economical protocols under greener pathways and following recent increased understanding of mechanistic aspects of Rh-catalyzed allylation via the hydrofunctionalization of allenes or alkynes, great strides have made in the design and development of new atom-economical protocols. In this article, we review this field from its beginning to current state.1 Introduction2 Rhodium-Catalyzed Allylic Substitution3 Rhodium-Catalyzed Allylation with Allenes4 Rhodium-Catalyzed Allylation with Alkynes5 Rhodium-Catalyzed Allylation with Dienes6 Rhodium-Catalyzed Allylation by ARO of Oxabicyclic Alkenes7 Rhodium-Catalyzed Enantioselective Allylation in Natural Product and Drug Synthesis8 Conclusion

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Section: Scheme 53 Rh-catalyzed Addition Of 13-dicarbonyl Compounds mentioning

confidence: 99%

Rhodium-Catalyzed Allylation Reactions

Thoke

Kang

2019

Synthesis

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“…Related reactions of internal alkynes were subsequently developed and applied to the synthesis of heterocycles (Scheme ) . In 2016, the groups of Dong and Breit simultaneously demonstrated that direct access to γ,δ‐unsaturated ketones may be achieved in decarboxylative coupling reactions of alkynes with β‐keto acids (Scheme ) ,…”

Section: Alkynes As Electrophilic π‐Allyl Precursorsmentioning

confidence: 99%

Alkynes as Electrophilic or Nucleophilic Allylmetal Precursors in Transition‐Metal Catalysis

et al. 2017

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Diverse late transition metal catalysts convert terminal or internal alkynes to transient allylmetal species that display electrophilic or nucleophilic properties. Whereas classical methods for the generation of allylmetal species often mandate formation of stoichiometric byproducts, recent use of alkynes as allylmetal precursors enables completely atom-efficient catalytic processes, including enantioselective transformations.

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“…However, since the first catalytic example was reported by Evans, different catalytic systems and electrophilic substrates have been developed to overcome the intrinsic instability of β ‐ketoacids . Among all methods explored so far, the Lewis acid catalysed decarboxylative additions of β ‐ketoacids are rare, only several reports about have been demonstrated with narrow scopes ,,,. Therefore, it is still highly desirable to develop reactions involving Lewis‐acid catalysed decarboxylative addition of β ‐ketoacids to new acceptors.…”

Section: Methodsmentioning

confidence: 99%