Taxamycins: a new enediyne family constructed from versatile disilyl-substituted building blocks

• Published in: Journal of organic chemistry Vol. 58; no. 16; pp. 4202 - 4204
• Main Authors: Lu, Yee Fung, Harwig, Curtis W, Fallis, Alex G
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 01.07.1993; Amer Chemical Soc
• Subjects: Alicyclic compounds; Alicyclic compounds, terpenoids, prostaglandins, steroids; Chemistry; Chemistry, Organic; Exact sciences and technology; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; SYSTEM; ESPERAMICINS; REAGENTS; POTENT ANTITUMOR ANTIBIOTICS; TAXOL; CHEMISTRY; CALICHEAMICINS; CORE STRUCTURE; AGLYCONES; CALICHEMICIN-GAMMA-1; Intramolecular reaction; Catalytic reaction; Condensation reaction; Nitrile; Aliphatic compound; Palladium Complexes; Silicon Organic compounds; Zerovalent metal Complexes; Aldehyde; Allylic compound; Enynic compound; Chemical coupling; Macrocycle; Bicyclic compound; Secondary alcohol; Monocyclic compound
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo00068a011

The Pd(0)-based synthesis of two disilyl synthons [(Z)-1-(trimethylsilyl)-6-(tert-butyldiphenylsilyl)hex-3-ene-1,5-diyne (7) and (Z)-1-(trimethylsilyl)-6-(triisopropylsilyl)hex-3-ene-1,5-diyne (8)], selective removal of the trimethylsilyl group (K2CO3, MeOH) to afford 13 and 14, and the construction of the taxamycin-12 compound 25 (16,17,18-trimethyl-2-(monomethyloxy)-9-hydroxybicyclo[9.3.1]pentadec-5-ene-3,7-diyne) by intramolecular Nozaki condensation of the iodoalkyne 24 (1,3,3-trimethyl-2-(2-oxoethyl)-4-((Z)-1-(monomethyloxy)-7-iodohept-4-ene-3,6-diynyl)cyclohexene) is described.