Stereochemical and mechanistic aspects of dioxygenase-catalysed benzylic hydroxylation of indene and chromane substrates


Autoria(s): Boyd, Derek; Sharma, Narain; Bowers, N.I.; Boyle, R.; Harrison, J.S.; Lee, K.; Bugg, T.D.H.; Gibson, D.T.
Data(s)

21/03/2003

Resumo

Toluene dioxygenase (TDO)-catalysed benzylic hydroxylation of indene substrates (8, 16 and 17), using whole cell cultures of Pseudomonas putida UV4, was found to yield inden-1-ol (14 and 22) and indan-1-one bioproducts (15 and 23). The formation of these bioproducts is consistent with the involvement of carbon-centred radical intermediates. TDO-catalysed oxidation of indenes 8 and 16 also gave cis-diols 13 and 18 respectively. TDO and naphthalene dioxygenase (NDO), used as both whole-cell preparations and as purified enzymes, were found to catalyse the benzylic hydroxylation of chromane 30, deuteriated (+/-)-chromane 30(D) and enantiomers (4S)-30(D) and (4R)-30(D) to yield (4R)- and (4S)-chroman-4-ols 31/31(D) respectively. The mechanism of benzylic hydroxylation of chromane 30/30(D) involves the stereoselective abstraction of a pro-R (with TDO) or a pro-S (with NDO) hydrogen atom at C-4 and a marked preference for retention of configuration.

Identificador

http://pure.qub.ac.uk/portal/en/publications/stereochemical-and-mechanistic-aspects-of-dioxygenasecatalysed-benzylic-hydroxylation-of-indene-and-chromane-substrates(01ae37e7-11b4-48be-af67-d2ad456b6b67).html

http://dx.doi.org/10.1039/b300898c

http://www.scopus.com/inward/record.url?scp=0141974850&partnerID=8YFLogxK

Idioma(s)

eng

Direitos

info:eu-repo/semantics/restrictedAccess

Fonte

Boyd , D , Sharma , N , Bowers , N I , Boyle , R , Harrison , J S , Lee , K , Bugg , T D H & Gibson , D T 2003 , ' Stereochemical and mechanistic aspects of dioxygenase-catalysed benzylic hydroxylation of indene and chromane substrates ' Organic and Biomolecular Chemistry , vol 1 , no. 8 , pp. 1298-1307 . DOI: 10.1039/b300898c

Palavras-Chave #/dk/atira/pure/subjectarea/asjc/1300 #Biochemistry, Genetics and Molecular Biology(all) #/dk/atira/pure/subjectarea/asjc/1600 #Chemistry(all)
Tipo

article