Center for Molecular Modeling - N. Piens

Reactivity of 3-oxo-β-lactams with respect to primary amines - an experimental and computational approach

wim — Wed, 16 Aug 2017 12:50:14 +0000

N. Piens, H. Goossens, D. Hertsen, S. Deketelaere, L. Crul, L. Demeurisse, J. De Moor, E. Van den Broeck, K. Mollet, K. Van Hecke, V. Van Speybroeck, M. D'Hooghe

Chemistry - A European Journal

2017 (23), 1-9

2017

Abstract

The reactivity of 3-oxo-β-lactams with respect to primary amines was investigated in depth. Depending on the specific azetidin-2-one C4 substituent, this reaction was shown to selectively produce 3-imino-β-lactams (through dehydration), α-aminoamides (through CO elimination) or ethanediamides (through an unprecedented C3-C4 ring opening). In addition to the experimental results, the mechanisms and factors governing these peculiar transformations were also examined and elucidated by means of density functional theory calculations.

DOI

http://dx.doi.org/10.1002/chem.201703852

Private attachment

Piens_et_al-2017-Chemistry_-_A_European_Journal.pdf

Synthesis of 2-Hydroxy-1,4-oxazin-3-ones through Ring Transformation of 3-Hydroxy-4-(1,2-dihydroxyethyl)--lactams and a Study of Their Reactivity

michel — Fri, 13 Jul 2012 11:46:22 +0000

K. Mollet, H. Goossens, N. Piens, S. Catak, M. Waroquier, V. Van Speybroeck, M. D'Hooghe, N. De Kimpe

Chemistry - A European Journal

19 (10), 3383-3396

2013

Abstract

The reactivity of 3-hydroxy-4-(1,2-dihydroxyethyl)-β-lactams with regard to the oxidant sodium periodate was evaluated, unexpectedly resulting in the exclusive formation of new 2-hydroxy-1,4-oxazin-3-ones through a C3C4 bond cleavage of the intermediate 4-formyl-3-hydroxy-β-lactams followed by a ring expansion. This peculiar transformation stands in sharp contrast with the known NaIO4-mediated oxidation of 3-alkoxy- and 3-phenoxy-4-(1,2-dihydroxyethyl)-β-lactams, which exclusively leads to the corresponding 4-formyl-β-lactams without a subsequent ring enlargement. In addition, this new class of functionalized oxazin-3-ones was further evaluated for its potential use as building blocks in the synthesis of a variety of differently substituted oxazin-3-ones, morpholin-3-ones and pyrazinones. Furthermore, additional insights into the mechanism and the factors governing this new ring-expansion reaction were provided by means of density functional theory calculations.

DOI

http://dx.doi.org/10.1002/chem.201203314

Private attachment

13_chem_eur_ j_19(10)3383_Mollet.pdf

Synthesis of 2-hydroxy-1,4-oxazin-3-ones through ring transformation of 3-hydroxy-4-(1,2-dihydroxyethyl)-β-lactams and study of their reactivity

samuel — Thu, 06 Feb 2020 11:35:52 +0000

N. Piens, K. Mollet, H. Goossens, S. Catak, M. Waroquier, K. Törnroos, V. Van Speybroeck, N. De Kimpe, M. D'Hooghe

ISBN/ISSN:

Talk

Conference / event / venue

12th Chemistry Conference for Young Scientists

Blankenberge, Belgium

Thursday, 27 February, 2014 to Friday, 28 February, 2014

Synthesis of 2-hydroxy-1,4-oxazin-3-ones through ring transformation of 3-hydroxy-4-(1,2-dihydroxyethyl)-β-lactams and study of their reactivity

samuel — Thu, 06 Feb 2020 11:30:01 +0000

N. Piens, K. Mollet, H. Goossens, S. Catak, M. Waroquier, K. Törnroos, V. Van Speybroeck, N. De Kimpe, M. D'Hooghe

ISBN/ISSN:

Talk

Conference / event / venue

17th Sigma-Aldrich Organic Synthesis Meeting

Blankenberge, Belgium

Thursday, 5 December, 2013 to Friday, 6 December, 2013

Computational Rationalization of the Ring Transformation of 3-hydroxy-4-(1,2-dihydroxyethyl)-β-lactams

catak — Mon, 22 Jul 2013 09:56:07 +0000

H. Goossens, S. Catak, K. Mollet, N. Piens, M. D'Hooghe, N. De Kimpe, M. Waroquier, V. Van Speybroeck

ISBN/ISSN:

Poster

Conference / event / venue

44th IUPAC World Chemistry Congress

Istanbul, Turkey

Sunday, 11 August, 2013 to Friday, 16 August, 2013

Abstract (private)

IUPACAbstract_Saron Catak.pdf