Literature DB >> 26553753

Radical [1,3] Rearrangements of Breslow Intermediates.

Sefat Alwarsh1, Yi Xu2, Steven Y Qian2, Matthias C McIntosh3.   

Abstract

Breslow intermediates that bear radical-stabilizing N substituents, such as benzyl, cinnamyl, and diarylmethyl, undergo facile homolytic C-N bond scission under mild conditions to give products of formal [1,3] rearrangement rather than benzoin condensation. EPR experiments and computational analysis support a radical-based mechanism. Implications for thiamine-based enzymes are discussed.
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Entities:  

Keywords:  Breslow intermediates; N-heterocyclic carbenes; radicals; rearrangement; thiamine

Mesh：

Substances：

Year:  2015        PMID： 26553753      PMCID： PMC4715472          DOI： 10.1002/anie.201508368

Source DB:  PubMed          Journal:  Angew Chem Int Ed Engl        ISSN： 1433-7851            Impact factor:   15.336


  19 in total

Review 1.  Organocatalysis by N-heterocyclic carbenes.

Authors:  Dieter Enders; Oliver Niemeier; Alexander Henseler
Journal:  Chem Rev       Date:  2007-10-23       Impact factor: 60.622

Review 2.  Thiamin diphosphate catalysis: enzymic and nonenzymic covalent intermediates.

Authors:  Ronald Kluger; Kai Tittmann
Journal:  Chem Rev       Date:  2008-05-21       Impact factor: 60.622

Review 3.  Organocatalytic Reactions Enabled by N-Heterocyclic Carbenes.

Authors:  Darrin M Flanigan; Fedor Romanov-Michailidis; Nicholas A White; Tomislav Rovis
Journal:  Chem Rev       Date:  2015-05-20       Impact factor: 60.622

4.  Unexpected tautomeric equilibria of the carbanion-enamine intermediate in pyruvate oxidase highlight unrecognized chemical versatility of thiamin.

Authors:  Danilo Meyer; Piotr Neumann; Eline Koers; Hanno Sjuts; Stefan Lüdtke; George M Sheldrick; Ralf Ficner; Kai Tittmann
Journal:  Proc Natl Acad Sci U S A       Date:  2012-06-22       Impact factor: 11.205

5.  Reactivity of intermediates in benzoylformate decarboxylase: avoiding the path to destruction.

Authors:  Qingyan Hu; Ronald Kluger
Journal:  J Am Chem Soc       Date:  2002-12-18       Impact factor: 15.419

Review 6.  Thiamin diphosphate-dependent enzymes: from enzymology to metabolic regulation, drug design and disease models.

Authors:  Victoria I Bunik; Adam Tylicki; Nikolay V Lukashev
Journal:  FEBS J       Date:  2013-10-16       Impact factor: 5.542

7.  Decomposition of 2-(1-hydroxybenzyl)thiamin. Ruling out stepwise cationic fragmentation.

Authors:  I F Moore; R Kluger
Journal:  Org Lett       Date:  2000-07-13       Impact factor: 6.005

8.  Assessment of experimental bond dissociation energies using composite ab initio methods and evaluation of the performances of density functional methods in the calculation of bond dissociation energies.

Authors:  Yong Feng; Lei Liu; Jin-Ti Wang; Hao Huang; Qing-Xiang Guo
Journal:  J Chem Inf Comput Sci       Date:  2003 Nov-Dec

9.  Characterization of the key intermediates of carbene-catalyzed umpolung by NMR spectroscopy and X-ray diffraction: breslow intermediates, homoenolates, and azolium enolates.

Authors:  Albrecht Berkessel; Veera Reddy Yatham; Silvia Elfert; Jörg-M Neudörfl
Journal:  Angew Chem Int Ed Engl       Date:  2013-08-28       Impact factor: 15.336

10.  Synthesis of enantiomerically pure N-(2,3-dihydroxypropyl)arylamides via oxidative esterification.

Authors:  Akula Raghunadh; Satish S More; T Krishna Chaitanya; Yadla Sateesh Kumar; Suresh Babu Meruva; L Vaikunta Rao; U K Syam Kumar
Journal:  Beilstein J Org Chem       Date:  2013-10-17       Impact factor: 2.883
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