122-73-6Relevant articles and documents
Site-Specific Alkene Hydromethylation via Protonolysis of Titanacyclobutanes
Bartfield, Noah M.,Frederich, James H.,Law, James A.
supporting information, p. 14360 - 14364 (2021/05/27)
Methyl groups are ubiquitous in biologically active molecules. Thus, new tactics to introduce this alkyl fragment into polyfunctional structures are of significant interest. With this goal in mind, a direct method for the Markovnikov hydromethylation of alkenes is reported. This method exploits the degenerate metathesis reaction between the titanium methylidene unveiled from Cp2Ti(μ-Cl)(μ-CH2)AlMe2 (Tebbe's reagent) and unactivated alkenes. Protonolysis of the resulting titanacyclobutanes in situ effects hydromethylation in a chemo-, regio-, and site-selective manner. The broad utility of this method is demonstrated across a series of mono- and di-substituted alkenes containing pendant alcohols, ethers, amides, carbamates, and basic amines.
Tandem ring-closing metathesis/transfer hydrogenation: Practical chemoselective hydrogenation of alkenes
Connolly, Timothy,Wang, Zhongyu,Walker, Michael A.,McDonald, Ivar M.,Peese, Kevin M.
, p. 4444 - 4447 (2015/01/09)
An operationally simple chemoselective transfer hydrogenation of alkenes using ruthenium metathesis catalysts is presented. Of great practicality, the transfer hydrogenation reagents can be added directly to a metathesis reaction and effect hydrogenation of the product alkene in a single pot at ambient temperature without the need to seal the vessel to prevent hydrogen gas escape. The reduction is applicable to a range of alkenes and can be performed in the presence of aryl halides and benzyl groups, a notable weakness of Pd-catalyzed hydrogenations. Scope and mechanistic considerations are presented.
Action of Boron Trifluoride on Aromatic Acetals
Alphonse, I.,Arulraj, S. J.
, p. 199 - 200 (2007/10/02)
Acetals of the type X-C6H4CH(OR)2 (where R = Et, n-Bu and isoamyl and X = H, CH3) react with boron trifluoride in anhyd. 1,2-dichloroethane to give benzyl alkyl ethers, α,β-unsaturated aldehydes and benzaldehyde.However, p-nitrobenzaldehyde di-n-butyl acetal gives only p-nitrobenzaldehyde.The formation of benzyl alkyl ethers is explained by a hydride ion transfer mechanism and that of α,β-unsaturated aldehyde by an aldol-type of condensation.