155397-12-9

Upstream product

• 630-18-2 tert-butyl isocyanide 
• 3839-31-4 dimethyl(phenyl)silyllithium 
• 507-19-7 t-butyl bromide 
• 201230-82-2 carbon monoxide 
• 185990-03-8 dimethylphenyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)silane 
• 3839-31-4 dimethyl(phenyl)silyl lithium 
• 70414-49-2 2,2-dimethyl-1-morpholinopropan-1-one 
• 598-98-1 Methyl pivalate 
• 768-33-2 phenyldimethylsilyl chloride 
• 3282-30-2 pivaloyl chloride 
• 155397-16-3 1,1-bis-2,2-dimethylpropan-1-ol 
• 24331-71-3 N,N-dimethylpivalamide 

Downstream Products

• 1240781-41-2 C₁₉H₃₀OSi 
• 1085202-82-9 C₂₁H₂₆OSi 

Relevant academic research and scientific papers

Cu-Catalyzed Carbonylative Silylation of Alkyl Halides: Efficient Access to Acylsilanes

A Cu-catalyzed carbonylative silylation of unactivated alkyl halides has been developed, enabling efficient synthesis of alkyl-substituted acylsilanes in high yield. A variety of functional groups are tolerated under the mild reaction conditions, and prim

Stereoselective syntheses of trisubstituted olefins via platinum catalysis: α-Silylenones with geometrical complementarity

The stereoselective syntheses of α-silylenones using catalytic PtCl2 are reported. Via alkyne activation, α- hydroxypropargylsilanes are converted to (Z)-silylenones through a highly selective silicon migration. The complementary (E)-silylenone

Can relief of ring-strain in a cyclopropylmethyllithium drive the Brook rearrangement?

α-Cyclopropyl-α-trialkylsilyl alkoxides were formed either by addition of cyclopropyllithiums to acylsilanes or by addition of organolithiums to a cyclopropylformylsilane. [1,2]-Brook rearrangement led to α-silyloxy organolithiums which on warming underwent cyclopropane ring opening and [1,5]-retro-Brook rearrangement to yield γ-silyl ketones. Despite the favourability of the cyclopropane ring opening, the Brook rearrangement still required the presence of an anion stabilising group to proceed. β-Silylketones were similarly formed by Brook-retro-Brook rearrangement on warming acylsilanes with a vinyllithium.

Efficient synthesis of acylsilanes using morpholine amides

(Chemical Equation Presented) A general synthesis of acylsilanes from the corresponding morpholine amides and silyllithium species is described. The use of morpholine amides is economical and prevents over-addition by the silyl nucleophile. The procedure cleanly affords acylsilanes in good yields and circumvents the use of stoichiometric copper(I) cyanide typically employed to synthesize these compounds from acid chlorides.

The reactions of phenyldimethylsilyllithium with nitriles

Phenyldimethylsilyllithium reacts with nitriles by several substantially different pathways depending upon the structure of the nitrile. The products include the acylsilane 2 from pivalonitrile (1), cumylsilane 5 from 2-phenylisobutyronitrile (4), the α-anion from phenylacetonitrile (9), and a mixture of benzil (15) and 2,4,5-triphenylimidazole (17) from benzonitrile (13).

Synthesis of Acylsilanes from Amides and Esters, and the Selective Oxidation of α-Silyl Alcohols to Aldehydes

The acylsilanes 2 can easily be made directly from the dimethylamides 3 by treatment with phenyldimethylsilyllithium.They can also be made in two steps from the esters 4 using 2 equiv. of phenyldimethylsilyllithium followed by oxidation of the disilyl alcohols 5 with PDC.The disilyl alcohols 5 can be used as intermediates in the conversion of esters into aldehydes without recourse to hydride reagents, by monodesilylation, using a Brook rearrangement, followed by oxidation and selective removal of the silyl group, using chromium trioxide in DMSO.