17718-97-7Relevant academic research and scientific papers
Reaction of silylketenes with carbanions: Simple preparation of α- silylketones using organocerium reagents
Akai, Shuji,Kitagaki, Shinji,Matsuda, Satoshi,Tsuzuki, Yasunori,Naka, Tadaatsu,Kita, Yasuyuki
, p. 1135 - 1139 (2007/10/03)
Preparation of α-silylketones 1 by the reaction of three kinds of silylketenes 3a-c with various organometallic reagents 4 was studied. Although the use of n-BuLi, MeMgBr, Me2CuLi, Et3Al, and Et2Zn resulted in complicated reactions, organocerium reagents 4 (M=CeCl2) added selectively to the carbonyl carbon of 3 to generate enolate anions A, which were treated with aqueous NH4Cl or alkyl halides 5 to give 1. Seventeen α-silylketones 1a-q were prepared in 3199% yields from three components, 3, alkyl- or arylcerium reagents 4, and proton or alkyl halides 5. This method was applied to a regiocontrolled preparation of two isomeric α-silylketones 1r, s.
RuCl2(PPh3)3: A new catalyst for diazocarbonyl insertions into heteroatom-hydrogen bonds
Sengupta, Saumitra,Das, Debasis,Sen Sarma, Debarati
, p. 8815 - 8818 (2007/10/03)
The first ever use of RuCl2(PPh3)3 as a catalyst for diazoketone insertions into heteroatom-hydrogen bonds is described.
A New and General Synthesis of α-Silyl Carbonyl Compounds by Si-H Insertion from Transition Metal Catalyzed Reactions of Diazo Esters and Diazo Ketones
Bagheri, Vahid,Doyle, Michael P.,Taunton, Jack,Claxton, E. Elizabeth
, p. 6158 - 6160 (2007/10/02)
α-Silyl esters and α-silyl ketones are formed in high yield by Rh2(OAc)4- or Cu(acac)2-catalyzed decomposition of diazo esters and diazo ketones in the presence of organosilanes.
A New Synthesis of β-Keto Phosphonates and β-Keto Silanes
Sampson, Paul,Hammond, Gerald B.,Wiemer, David F.
, p. 4342 - 4347 (2007/10/02)
A new preparation of β-keto phosphonates from α-bromo ketones, by reaction of dialkyl chlorophosphate electrophiles with the dilithiated derivative of the bromo ketone, is described.This umpolung approach is complementary to the classical Arbuzov synthesis in two important ways.It extends the range of possible ketone substrates, allowing use of secondary α-halo ketones or α-bromo ketones where the Arbuzov reaction often fails.It also extends the variety of phosphonates available, by allowing, for example, the direct preparation of bis-(trifluoroethyl)phosphonates.These fluoroalkyl phosphonates are not readily available via the Arbuzov reaction,because tris(trifluoroethyl) phosphite is only weakly nucleophilic.From our efforts to employ (trialkylsiloxy)vinyl bromides and n-butyllithium to generate an intermediate vinyllithium reagent, in place of forming the lithium enolate and using tert-butyllithium, a facile migration of trialkylsilyl groups from oxygen to the α-carbon has been discovered.This has been exploited in the development of a new route from α-bromo ketones to α-trialkylsilyl ketones.
α-Trialkylsilylketones from α-Bromoketones: Utilization of a 1,3-O to C Silyl Migration
Sampson, Paul,Wiemer, David F.
, p. 1746 - 1747 (2007/10/02)
A new route from α-bromoketones to α-trialkylsilylketones has been developed which demonstrates the viability of halogen-metal exchange vis-a-vis nucleophilic attack at silicon, even with the unhindered trimethylsilyl group.
