Universität zu Köln

Griesbeck, Axel G., Goldfuss, Bernd ORCID: 0000-0002-1814-8818, Jaeger, Christina, Bruellingen, Eric, Lippold, Tim and Kleczka, Margarethe (2017). Strong Asymmetry in the Perepoxide Bifurcation Mechanism: The Large-Group Effect in the Singlet Oxygen Ene Reaction with Allylic Alcohols. ChemPhotoChem, 1 (5). S. 213 - 222. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 2367-0932

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Abstract

The singlet oxygen reactions of sterically crowded allylic alcohols result in the preferential formation of g-hydroperoxy alcohols with regioselectivities up to 98:2. The kinetic cis effect still prevails in the first, rate-determining step of this two-step non-intermediate ene mechanism (k(E-5)/k(Z-5)=1.9). The primary allylic alcohol 3 showed no regioselectivity at all, increasing the steric demands at the a carbon and directing the singlet oxygen addition towards the gamma carbon up to 98:2 regioselectivity. DFT calculations rationalized these results and show the decisive role of the symmetry-breaking bifurcation following the early transition states. The use of the products as substrates for the synthesis of five-and seven-membered ring peroxides, namely 4-methylene-1,2-dioxolanes and 6-methylene-1,2,4-trioxepanes, by rare earth metal complexes as Lewis acids is also demonstrated.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Griesbeck, Axel G. UNSPECIFIED UNSPECIFIED UNSPECIFIED Goldfuss, Bernd UNSPECIFIED orcid.org/0000-0002-1814-8818 UNSPECIFIED Jaeger, Christina UNSPECIFIED UNSPECIFIED UNSPECIFIED Bruellingen, Eric UNSPECIFIED UNSPECIFIED UNSPECIFIED Lippold, Tim UNSPECIFIED UNSPECIFIED UNSPECIFIED Kleczka, Margarethe UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-231525
DOI:	10.1002/cptc.201600041
Journal or Publication Title:	ChemPhotoChem
Volume:	1
Number:	5
Page Range:	S. 213 - 222
Date:	2017
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	2367-0932
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language ZETA VALENCE QUALITY; BASIS-SETS; PHOTOOXYGENATION; O-1(2); SELECTIVITY; SULFOXIDES; OXIDATION; ALKENES Multiple languages Chemistry, Physical Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/23152