One‐Step Catalytic Asymmetric Synthesis of Configurationally Stable Tröger Bases

Sharma, Ankit; Guénée, Laure; Naubron, Jean-Valère; Lacour, Jérôme

doi:10.1002/anie.201100134

Cited by 68 publications

(35 citation statements)

References 47 publications

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“…were obtained from aryl substituents of aryldiazoacetates in the rhodium acetate catalyzed reactions of configurationally stable Tröger bases. 11 Our proposed mechanism for oxonium ylide formation from 1 and subsequent [1,2]-Stevens rearrangement (Scheme 1) that suggests a concerted reaction is in conflict with a homolytic/heterolytic cleavage/recombination mechanism (i.e., absence of substituent effects, and steric influence on stereo-selectivity), although a very fast cleavage/recombination process that is barely distinguishable from a concerted reaction is also possible. We now report analogous investigations with compounds that are structurally similar to 1 whose oxonium ylides could undergo symmetry-allowed [2,3]-sigmatropic rearrangements that are not subject to orbital symmetry restrictions.…”

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confidence: 92%

Competitive [2,3]- and [1,2]-Oxonium Ylide Rearrangements. Concerted or Stepwise?

et al. 2012

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The axial-equatorial conformational isomer distribution of the reactant diazoacetoacetate or its metal carbene intermediate is reflected in Rh(II) catalyzed oxonium ylide forming reactions of 3-(trans-2-arylvinyl)tetrahydropyranone- 5-diazoacetoacetates that afford diastereoisomeric products for both the symmetry-allowed [2,3]- and the formally symmetry-forbidden [1,2]-oxonium ylide rearrangements.

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confidence: 92%

Competitive [2,3]- and [1,2]-Oxonium Ylide Rearrangements. Concerted or Stepwise?

et al. 2012

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“…(G) Lacour et al 12 reported a one-step catalytic asymmetric synthesis of ethano-Tröger's base using ethyl 2-diazoacetoacetate and a rhodium(II)-catalyzed reaction. A new carbon quaternary stereogenic center was introduced.…”

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confidence: 99%

Ethyl 2-Diazoacetoacetate

Dias

2013

Synlett

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This feature focuses on a reagent chosen by a postgraduate, highlighting the uses and preparation of the reagent in current research spotlight Ethyl 2-Diazoacetoacetate Compiled by Flaviana Rodrigues Fintelman DiasFlaviana Rodrigues Fintelman Dias was born in Muriaé, Brazil in 1985. She received her pharmacy degree from Universidade Federal Fluminense (UFF), Niterói, Brazil in 2010. She is currently in the final stages of her M.Sc. studies under the supervision of the Professors Anna Claudia Cunha and Vitor Francisco Ferreira in organic chemistry at Universidade Federal Fluminense. Her research interests are focused on the design and synthesis of new bioactive compounds, such as quinone and 1,2,3-triazole derivatives. By using ethyl 2-diazoacetoacetate and para-substituted aromatic hydrazine hydrochlorides several 1,2,3-triazoles have been prepared.

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“…A metalfree carbene approach to derivatize brucine was recently reported, which yielded a ring-expanded product through formation of an aza-ylide species followed by a [1,2]-Stevens rearrangement 34 . Indeed, the use of metallocarbenoids to access an aza-ylide intermediate followed by ring expansion has been widely described [35][36][37] . Interested in effecting C-H insertions via a carbenoid approach, we were intrigued as to whether the presence of a suitable rhodium catalyst and appropriate temperature might influence the nature of the reaction with brucine, allowing for C-H insertion over aza-ylide formation or catalyst poisoning, despite the presence of the nucleophilic amine.…”

Section: Resultsmentioning

confidence: 99%

Late-stage C–H functionalization of complex alkaloids and drug molecules via intermolecular rhodium-carbenoid insertion

et al. 2015

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Alkaloids constitute a large family of natural products possessing diverse biological properties. Their unique and complex structures have inspired numerous innovations in synthetic chemistry. In the realm of late-stage C-H functionalization, alkaloids remain a significant challenge due to the presence of the basic amine and a variety of other functional groups. Herein we report the first examples of dirhodium(II)-catalysed intermolecular C-H insertion into complex natural products containing nucleophilic tertiary amines to generate a C-C bond. The application to a diverse range of alkaloids and drug molecules demonstrates remarkable chemoselectivity and predictable regioselectivity. The capacity for late-stage diversification is highlighted in the catalyst-controlled selective functionalizations of the alkaloid brucine. The remarkable selectivity observed, particularly for site-specific C-H insertion at N-methyl functionalities, offers utility in a range of applications where efficient installation of synthetic handles on complex alkaloids is desired.

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One‐Step Catalytic Asymmetric Synthesis of Configurationally Stable Tröger Bases

Cited by 68 publications

References 47 publications

Competitive [2,3]- and [1,2]-Oxonium Ylide Rearrangements. Concerted or Stepwise?

Competitive [2,3]- and [1,2]-Oxonium Ylide Rearrangements. Concerted or Stepwise?

Ethyl 2-Diazoacetoacetate

Late-stage C–H functionalization of complex alkaloids and drug molecules via intermolecular rhodium-carbenoid insertion

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