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:
CreatorsEmailORCIDORCID Put Code
Griesbeck, Axel G.UNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Goldfuss, BerndUNSPECIFIEDorcid.org/0000-0002-1814-8818UNSPECIFIED
Jaeger, ChristinaUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Bruellingen, EricUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Lippold, TimUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Kleczka, MargaretheUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
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:
KeywordsLanguage
ZETA VALENCE QUALITY; BASIS-SETS; PHOTOOXYGENATION; O-1(2); SELECTIVITY; SULFOXIDES; OXIDATION; ALKENESMultiple languages
Chemistry, PhysicalMultiple languages
Refereed: Yes
URI: http://kups.ub.uni-koeln.de/id/eprint/23152

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