Universität zu Köln

Mandic, Leo, Mlinaric-Majerski, Kata ORCID: 0000-0001-6282-1662, Griesbeck, Axel G. ORCID: 0000-0002-6546-3482 and Basaric, Nikola ORCID: 0000-0001-9412-9734 (2016). Photodecarboxylation of Adamantane Amino Acids Activated by Phthalimide. Eur. J. Org. Chem., 2016 (25). S. 4404 - 4415. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1099-0690

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Abstract

Adamantane alpha-, beta-, and delta-amino acids activated by phthalimide (i.e., 3-6) were synthesized, and their photochemical reactivities were investigated. Amino acid derivatives 3-6 underwent a photoinduced electron transfer (PET) and decarboxylation reaction sequence, most probably through a triplet excited state. The decarboxylations of the beta-amino acid derivatives were succeeded by cyclization reactions that afforded complex polycyclic molecules with potential biological interest. The adamantyl radical that is produced by the photoinduced decarboxylation could be trapped by alkenes or oxygen to deliver adducts or alcohols, respectively. The photodecarboxylation process was shown to be more efficient under acetone sensitization conditions (with quantum yields, Phi = 0.02-0.5) than upon direct excitation, and the reactivity was dependent on the chain length (intramolecular distance) between the electron donor (carboxylate) and acceptor (phthalimide in the triplet excited state) of the derivative. The formation of different radicals, that is, the 1- or 2-adamantyl intermediate, probably does not affect the overall rate of the decarboxylation This current report provides a better understanding of photodecarboxylation and the rational design of molecular systems to undergo photoinduced decarboxylation and cyclization reactions.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Mandic, Leo UNSPECIFIED UNSPECIFIED UNSPECIFIED Mlinaric-Majerski, Kata UNSPECIFIED orcid.org/0000-0001-6282-1662 UNSPECIFIED Griesbeck, Axel G. UNSPECIFIED orcid.org/0000-0002-6546-3482 UNSPECIFIED Basaric, Nikola UNSPECIFIED orcid.org/0000-0001-9412-9734 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-264349
DOI:	10.1002/ejoc.201600491
Journal or Publication Title:	Eur. J. Org. Chem.
Volume:	2016
Number:	25
Page Range:	S. 4404 - 4415
Date:	2016
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	1099-0690
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 ANTIVIRAL ACTIVITY EVALUATION; LASER FLASH-PHOTOLYSIS; 2-ADAMANTYL RADICALS; CARBOXYLIC-ACIDS; RING EXPANSION; KETOPROFEN; PHOTOCHEMISTRY; SINGLET; BENZYLATIONS; SPECTROSCOPY Multiple languages Chemistry, Organic Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/26434