5350-55-0

Upstream product

• 100-94-7 dimethyldibenzylammonium chloride 
• 41870-52-4 α-phenyl-o-methylbenzyl chloride 
• 124-40-3 dimethyl amine 
• 16536-62-2 N-benzyl-N,N-dimethylphenylmethylammonium bromide 
• 103-83-3 N,N'-dimethylbenzylamine 
• 6639-19-6 N,N,2-trimethylbenzamide 
• 100-58-3 phenylmagnesium bromide 
• 100-39-0 benzyl bromide 
• 68-12-2 N,N-dimethyl-formamide 
• 100-44-7 benzyl chloride 
• 932-31-0 ortho-tolylmagnesium bromide 
• 827-36-1 2-(N,N-dimethylamino)-2-phenylacetonitrile 

Downstream Products

• 102559-28-4 dimethyl-(2-methyl-benzhydryl)-amine oxide 

Relevant academic research and scientific papers

Transition-Metal-Free Reductive Functionalization of Tertiary Carboxamides and Lactams for α-Branched Amine Synthesis

A new method for the synthesis of α-branched amines by reductive functionalization of tertiary carboxamides and lactams is described. The process relies on the efficient and controlled reduction of tertiary amides by a sodium hydride/sodium iodide composite, in situ treatment of the resulting anionic hemiaminal with trimethylsilyl chloride and subsequent coupling with nucleophilic reagents including Grignard reagents and tetrabutylammonium cyanide. The new method exhibits broad functional-group compatibility, operates under transition-metal-free reaction conditions, and is suitable for various synthetic applications on both sub-millimole and on multigram scales.

Benzylation Reactions in DMF Lead to an Impurity Which Acts as an Organocatalyst Poison in Thiourea-Catalyzed Glycosylations

The benzylation of alcohols with the commonly used combination of benzyl bromide and sodium hydride in DMF can lead to the formation of an amine side product, N,N′-dimethyl-1-phenyl-1-(o-tolyl)methanamine. This amine coeluted with benzylated galactal during column chromatography and was found to be a catalyst poison in thiourea-catalyzed glycosylations of galactals. It may also be problematic for other base-sensitive reactions involving benzylated substrates. Solutions to this problem are described.

Application of 13C NMR Spectroscopy and 13C-Labeled Benzylammonium Salts to the Study of Rearrangements of Ammonium Benzylides

Ylides generated from N-(cyanomethyl)-N,N-dimethyl-N-[α-(trimethylsilyl)benzyl]ammonium chloride (4) and fluoride anion afford the products of [1,2] shift 11 and [2,3] shift 13. Formation of product 13 shows that, in the presence of water from TBAF, rearrangements and [1,3]H shift in ylide intermediates become competitive processes. The reaction of N-benzyl-N,N-dimethyl-N-[α-(trimethylsilyl)benzyl]ammonium bromide (5) and 13C labeled (at the benzyl carbon) salt 5* gave a mixture of 10, 14, and 15 as products of [1,4], [1,2], and [2,3] rearrangement, respectively. 13C NMR spectra of products derived from salt 5* exclude [1,3]H shift in ylide 9a+-. Rearrangement of ylides generated from N-benzyl-N,N-dimethyl-N-[(dimethylphenylsilyl)methyl]ammonium bromide (6*) (enriched in 13C at benzyl carbon) and n-BuLi reveals that N,N-dimethyl-2-[(dimeth-ylphenylsilyl)methyl]benzylamine (20*) is not formed by a [1,4] shift but instead, via a [2,3] shift in silylmethylide followed by subsequent [1,4]Si and [1,2]H shift, as previously suggested in the literature. This mechanism is unique to some silyl-substituted ylides.