Literature DB >> 19397300

Anti-selective epoxidation of methyl alpha-methylene-beta-tert-butyldimethylsilyloxycarboxylate esters. Evidence for stereospecific oxygen atom transfer in a nucleophilic epoxidation process.

Jakub Svenda1, Andrew G Myers.   

Abstract

Methyl alpha-methylene-beta-tert-butyldimethylsilyloxycarboxylate esters are found to undergo diastereoselective epoxidation in the presence of potassium tert-butoxide-tert-butyl hydroperoxide to form anti products. In an effort to better understand mechanistic details of the transformation and the basis of diastereoselectivities observed, we studied the epoxidation of substrates with alpha-methylene groups containing (trans) deuterium labels and discovered that oxygen-atom transfer proceeds with > or = 95% stereospecificity in all cases examined. These and other experiments suggest that the mechanism of epoxidation is not distinguishable from a concerted process.

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Year:  2009        PMID： 19397300      PMCID： PMC2766803          DOI： 10.1021/ol900665a

Source DB:  PubMed          Journal:  Org Lett        ISSN： 1523-7052            Impact factor:   6.005


  5 in total

1.  Stereoselective epoxidations of acyclic allylic alcohols by transition metal--hydroperoxide reagents. Synthesis of dl-C18 Cecropia juvenile hormone from farnesol.

Authors:  S Tanaka; H Yamamoto; H Nozaki; K B Sharpless; R C Michaelson; J D Cutting
Journal:  J Am Chem Soc       Date:  1974-08-07       Impact factor: 15.419

2.  Trans- and cis-selective Lewis acid catalyzed hydrogermylation of alkynes.

Authors:  Todd Schwier; Vladimir Gevorgyan
Journal:  Org Lett       Date:  2005-11-10       Impact factor: 6.005

3.  The isomerisation of (Z)-3-[2H1]-phenylprop-2-enone as a measure of the rate of hydroperoxide addition in Weitz-Scheffer and Julia-Colonna epoxidations.

Authors:  David R Kelly; Eva Caroff; Robert W Flood; William Heal; Stanley M Roberts
Journal:  Chem Commun (Camb)       Date:  2004-08-25       Impact factor: 6.222

4.  Quantitative DFT modeling of the enantiomeric excess for dioxirane-catalyzed epoxidations.

Authors:  Severin T Schneebeli; Michelle Lynn Hall; Ronald Breslow; Richard Friesner
Journal:  J Am Chem Soc       Date:  2009-03-25       Impact factor: 15.419

5.  Isotope effects and the mechanism of epoxidation of cyclohexenone with tert-butyl hydroperoxide.

Authors:  Chad F Christian; Tetsuya Takeya; Michael J Szymanski; Daniel A Singleton
Journal:  J Org Chem       Date:  2007-07-03       Impact factor: 4.354
  5 in total
  3 in total

1.  An Oxy-anion Accelerated [1,5]-o-Quinone Methide Shift During the Nucleophilic Epoxidation of Salicylfulvene.

Authors:  Mingwei Yang; John Basada; Scott Gronert; Ihsan Erden
Journal:  European J Org Chem       Date:  2019-12-11

2.  A multiply convergent platform for the synthesis of trioxacarcins.

Authors:  Jakub Švenda; Nicholas Hill; Andrew G Myers
Journal:  Proc Natl Acad Sci U S A       Date:  2011-01-18       Impact factor: 11.205

3.  Asymmetric total synthesis of (-)-plicatic acid via a highly enantioselective and diastereoselective nucleophilic epoxidation of acyclic trisubstitued olefins.

Authors:  Bing-Feng Sun; Ran Hong; Yan-Biao Kang; Li Deng
Journal:  J Am Chem Soc       Date:  2009-08-05       Impact factor: 15.419
  3 in total

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