Synthesis of a phosphapyracene via metal-mediated cyclization: structural and reactivity effects of acenaphthene precursors

Autor:	David S. Glueck, Christopher J. A. Daley, Arnold L. Rheingold, Ge Wang, James A. Golen, Marites A. Guino-o
Rok vydání:	2015
Předmět:	Acenaphthene Medicinal chemistry Catalysis Inorganic Chemistry Metal chemistry.chemical_compound Deprotonation chemistry visual_art visual_art.visual_art_medium Organic chemistry Reactivity (chemistry) Trifluoromethanesulfonate Phosphine Naphthalene
Zdroj:	Dalton Transactions. 44:9943-9954
ISSN:	1477-9234 1477-9226
DOI:	10.1039/c5dt00520e
Popis:	Metal-mediated synthesis of a new heterocycle, 1-phenyl-phosphapyracene (Ph-4, Ph-PyraPhos), by tandem phosphination/cyclization of peri-substituted 5-bromo-6-chloromethylacenaphthene (3) was investigated for comparison to Pt-catalyzed formation of 1-phosphaacenaphthenes (2, AcePhos) from the analogous naphthalene precursor (1). Reaction of PH2Ph with 3, NaOSiMe3 and a Cu catalyst gave Ph-4; a Pt catalyst yielded PHPh(CH2Ar) (Ph-11, Ar = 5-Br-acenaphthyl). Deprotonation of a complex of this secondary phosphine, [Pt((R,R)-Me-DuPhos)(Ph)(PHPh(CH2Ar))][PF6] (17), generated the phosphido intermediate Pt((R,R)-Me-DuPhos)(Ph)(PPhCH2Ar) (Ph-8), which cyclized to give [Pt((R,R)-Me-DuPhos)(Ph)(Ph-PyraPhos)][PF6] (18). Treatment of Ph-8 with silver triflate gave 18 and the cyclometalated phosphine complex [Pt((R,R)-Me-DuPhos)(κ2-(P,C)-5-Ph2PCH2-6-C12H8)][PF6] (21), which might form via Pt(IV) intermediates. The effects of the added “ace” bridge on structure and reactivity are discussed.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::af9437692767d4769dfaf5a718bfade7 https://doi.org/10.1039/c5dt00520e Zobrazit plný text záznamu