7302-03-6Relevant articles and documents
Preparation and reactions of monocyclic bis(cyclopentadienyl)titanacyclopentenes and -pentadienes
Sato, Kimihiko,Nishihara, Yasushi,Huo, Shouquan,Xi, Zhenfeng,Takahashi, Tamotsu
, p. 18 - 26 (2007/10/03)
A combination of Cp2TiCl2-2EtMgBr was found to be very effective for the formation of monocyclic titanacyclopentenes in excellent yields. On the other hand, a combination of Cp2TiCl2-2n-BuLi was used for intermolecular coupling of two alkynes to form titanacyclopentadienes in good to excellent yields. A reaction temperature range from -10 to -30°C was critical for the success of the combinations. Reactions of these in situ-prepared titanacycles show interesting similarities to or differences from their zirconacycle analogs.
New nickel-catalyzed carbozincation of alkynes: A short synthesis of (Z)-tamoxifen
Studemann,Knochel
, p. 93 - 95 (2007/10/03)
A new highlight in the repertoire of carbometalation reactions is the highly stereo- and regioselective nickel-catalyzed carbozincation of internal alkynes. This is exemplified by a short and effective synthesis of the anti-breast-cancer drug (Z)-tamoxifen. This reaction also allows the stereoselective synthesis of various tri- and tetrasubstituted olefins in good yield.
Polylithiumorganic compounds -19. Regioselective carbon-carbon σ-bond scission followed by a 1,6-proton shift upon the reductive metalation of benzylidenecyclopropane derivatives with lithium metal
Maercker, Adalbert,Daub, Volker E. E.
, p. 2439 - 2458 (2007/10/02)
Depending on the substituent α-substituted benzylidenecyclopropanes (32) react more or less readily with lithium dust (2% sodium) in diethyl ether whereby a regioselective scission of only the cyclopropane σ-bond cis to the phenyl ring takes place. Upon raising the temperature the primarily formed 1,3-dilithiumorganic compound due to an agostic interaction rearranges by a 1,6-proton shift into a doubly bridged 1,4-dilithio compound. With α-methylbenzylidenecyclopropane (32c) this rearrangement was shown to occur intermolecularly via a trilithiumorganic compound 56. The suggested mechanism of these reductive metalation reactions via a bisected radical anion 87 where the lithium is mainly bound to the cyclopropyl carbon atom and oriented syn to the phenyl ring, was supported by MNDO (geometries) and ab initio (energies) calculations.