Ligand Control in Enantioselective Desymmetrization of Bicyclic Hydrazines: Rhodium(I)‐Catalyzed Ring‐Opening <i>versus</i> Hydroarylation

Panteleev, Jane; Ménard, Fréderic; Lautens, Mark

doi:10.1002/adsc.200800587

Cited by 84 publications

(13 citation statements)

References 57 publications

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“…To the best of our knowledge, only two examples involving 1,4-metal migration over irreversible β-X elimination have been reported so far. Selective 1,4-rhodium migration over β-nitrogen elimination was achieved by the Lautens group on arylative desymmetrization of diazabicycles, and selective 1,4-palladium migration over β-nitrogen elimination was reported by Loh and Xu in the palladium-catalyzed diverse transformations of N -vinyl-acetamides . To further exploit the potential of 1,4-metal migration in synthesis, novel 1,4-metal migrations are still highly desirable.…”

mentioning

confidence: 99%

Rhodium-Catalyzed Expeditious Synthesis of Indenes from Propargyl Alcohols and Organoboronic Acids by Selective 1,4-Rhodium Migration over β-Oxygen Elimination

et al. 2019

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An expeditious synthetic route to 1,1-disubstituted indenes from propargyl alcohols and organoboronic acids was developed under rhodium catalysis, and selective 1,4-rhodium migration over β-oxygen elimination was involved as the key step. DPEphos was found to be crucial to promote the transformation, and density functional theory (DFT) calculations indicated that DPEPhos can lower the relative energy of the key intermediate on the 1,4-migration path, leading to the unusual selectivity.

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confidence: 99%

Rhodium-Catalyzed Expeditious Synthesis of Indenes from Propargyl Alcohols and Organoboronic Acids by Selective 1,4-Rhodium Migration over β-Oxygen Elimination

et al. 2019

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“…The amino substituent, the nature of the substituent on arylboronic acid, the type of Rh-catalyst, and the experimental reaction conditions all influenced the reaction outcome. 214 The yields of the reactions strongly depend on the specific substituent patterns of the reagents used. Although the scope of the reaction requires should be elaborated upon in more detail, this direct strategy allows rapid access to the 2-arylethanesulfonamide chemotype.…”

Section: Table 48mentioning

confidence: 99%

Rh-catalyzed asymmetric 1,4-addition reactions to α,β-unsaturated carbonyl and related compounds: an update

Heravi

Dehghani

Zadsirjan

2016

Tetrahedron: Asymmetry

106

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Rh-catalyzed asymmetric 1,4-addition reactions to a,b-unsaturated carbonyl and related compounds: an update Available online xxxx Dedicated to my son, OMID on the occasion of his 35th birthday. a b s t r a c tThe Rh-catalyzed asymmetric 1,4-addition of organometallic reagents to an appropriate receptor has been a growing area of research over the last decade. The receptors for such a 1,4-addition reaction are chiefly a,b-unsaturated ketones, esters, amides, enones, nitroalkenes, and occasionally phosphonates etc. This reaction in the presence of chiral rhodium complexes introduce the aryl and alkenyl groups at the b-position of the above electron poor olefins, enantioselectively. Chiral Rh complexes similar to other transition metals can be added to some electron poor olefins, in turn making them viable to attack by various organometallic reagents for highly enantioselective C-C bond formation. The Rh-catalyzed asymmetric 1,4-addition of organometallic reagents to electron poor olefins has been reviewed in 2003. Due to the importance of the asymmetric C-C bond formation via 1,4-conjugate addition reactions and the number of such reactions catalyzed by Rh-complexes, in this review we highlight the recent advances in Rh-complex asymmetric catalyzed 1,4-addition reactions since 2003.

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“…Interestingly, when the ortho ‐hydrogen with respect to the boronic acid is sufficiently activated by a heteroatom, an oxidative C−H insertion of the rhodium followed by reductive elimination and protonation afforded reductive arylation products without ring opening (Scheme 17, eq. a) [62,65] . In 2010 Lautens and Bexrud applied a related asymmetric hydroarylation of bicyclic hydrazines catalysed by a chiral rhodium N‐heterocyclic carbene complex to give an alternative route to N‐Boc protected alkaloid epibatidine [66] .…”

Section: Boronic Acids and Derivativesmentioning

confidence: 99%

Boron Reagents and Catalysts for the Functionalization of Strained Heterocycles

Pineschi

2021

Adv Synth Catal

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The particular nature of boron compounds allows an ample modularity of their properties ranging from Lewis acids, C‐nucleophiles, B‐nucleophiles, or even conjunctive reagents for new synthetic manipulations. Moreover, the increasing demand for functionalized boron derivatives for pharmaceutical or material science applications requires the development of new synthetic methods for boron introduction in organic compounds. This review summarizes the possible combinations of boron derivatives with a variety of strained heterocycles reported in the most recent literature.

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Ligand Control in Enantioselective Desymmetrization of Bicyclic Hydrazines: Rhodium(I)‐Catalyzed Ring‐Opening versus Hydroarylation

Cited by 84 publications

References 57 publications

Rhodium-Catalyzed Expeditious Synthesis of Indenes from Propargyl Alcohols and Organoboronic Acids by Selective 1,4-Rhodium Migration over β-Oxygen Elimination

Rhodium-Catalyzed Expeditious Synthesis of Indenes from Propargyl Alcohols and Organoboronic Acids by Selective 1,4-Rhodium Migration over β-Oxygen Elimination

Rh-catalyzed asymmetric 1,4-addition reactions to α,β-unsaturated carbonyl and related compounds: an update

Boron Reagents and Catalysts for the Functionalization of Strained Heterocycles

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