155397-24-3Relevant academic research and scientific papers
α-Amino carbene or carbenoid formation in the reaction of a tertiary amide with PhMe2SiLi and its insertion into the Si-Li bond of a second equivalent
Fleming, Ian,Mack, Stephen R.,Clark, Barry P.
, p. 713 - 714 (1998)
PhMe2SiLi reacts with tertiary amides, RCONMe2, to give a carbene, RCNMe2, or an equivalent carbenoid, which gives enediamines, R(Me2N)C=C(NMe2)R, in the absence of a strong nucleophile, but is attacked by strong nucleophiles, NuLi, to give lithium reagents R(Me2N)CLiNu.
Cu-Catalyzed Carbonylative Silylation of Alkyl Halides: Efficient Access to Acylsilanes
Cheng, Li-Jie,Mankad, Neal P.
supporting information, p. 80 - 84 (2020/01/09)
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
Regio- and Stereoselective Synthesis of Fully Substituted Silyl Enol Ethers of Ketones and Aldehydes in Acyclic Systems
Wang, Peter-Yong,Duret, Guillaume,Marek, Ilan
supporting information, p. 14995 - 14999 (2019/09/17)
The regio- and stereoselective preparation of fully substituted and stereodefined silyl enol ethers of ketones and aldehydes through an allyl-Brook rearrangement is reported. This fast and efficient method proceeds from a mixture of E and Z isomers of easily accessible starting materials.
Efficient synthesis of acylsilanes using morpholine amides
Clark, Christopher T.,Milgram, Benjamin C.,Scheidt, Karl A.
, p. 3977 - 3980 (2007/10/03)
(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.
1,1-Disilyl alcohols as d1 synthons: Harnessing the 1,2-Brook rearrangement
Fleming, Ian,Lawrence, Annabel J.,Richardson, Robert D.,Surry, David S.,West, Mark C.
, p. 3349 - 3365 (2007/10/03)
1,1-Disilyl alcohols like 6 give the silyl ethers like 9 on treatment with base and alkyl halides, in a reaction which may be formulated as the alkylation of the Brook-rearranged carbanion 8. The products can be oxidised to give ketones like 10, showing that this Brook-rearranging system supplies a controlled d1 synthon of the acyl anion class. The alcohols can be prepared from the acid chloride 12 and dimethyl(phenyl)silyllithium, but the intermediate anion 21 need not be worked up; it can be used directly in the alkylation step.
Synthesis of Acylsilanes from Amides and Esters, and the Selective Oxidation of α-Silyl Alcohols to Aldehydes
Fleming, Ian,Ghosh, Usha
, p. 257 - 262 (2007/10/02)
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.
