Selective preparation of benzyltitanium compounds by the metalative Reppe reaction. Its application to the first synthesis of alcyopterosin A.
Dialkoxytitanacyclopentadienes, prepared from two different acetylenes and a divalent titanium alkoxide reagent, Ti(O-i-Pr)4/2 i-PrMgCl, reacted with propargyl bromide to give directly benzyltitanium compounds. The resultant benzyltitanium compounds underwent deuteriolysis, iodinolysis (with I2), or oxygenation (with O2 gas) to give the corresponding deuterium-labeled compounds, iodides, or alcohols, illustrating their synthetic versatility. The first synthesis of alcyopterosin A, a bicyclic aromatic sesquiterpenoid recently isolated and characterized, has been achieved by this method, starting with an appropriate combination of an acetylene and a diyne.
Tanaka
Ryoichi
R
Department of Biological Information, Graduate School of Bioscience and Biotechnology, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8501, Japan.
Nakano
Yoshitaka
Y
Suzuki
Daisuke
D
Urabe
Hirokazu
H
Sato
Fumie
F
D001593:Benzyl Compounds / Q000138:chemical synthesis / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D012717:Sesquiterpenes / Q000138:chemical synthesis*; D014025:Titanium / Q000737:chemistry*
D001593:Benzyl Compounds; D009942:Organometallic Compounds; D012717:Sesquiterpenes; C466487:alcyopterosin A; D014025:Titanium