35155-66-9Relevant articles and documents
C-O Bond Activation as a Strategy in Palladium-Catalyzed Cross-Coupling
Becica, Joseph,Leitch, David C.
, p. 641 - 646 (2020/12/14)
The activation of strong C-O bonds in cross-coupling catalysis can open up new oxygenate-based feedstocks and building blocks for complex-molecule synthesis. Although Ni catalysis has been the major focus for cross-coupling of carboxylate-based electrophiles, we recently demonstrated that palladium catalyzes not only difficult C-O oxidative additions but also Suzuki-Type cross-couplings of alkenyl carboxylates under mild conditions. We propose that, depending on the reaction conditions, either a typical Pd(0)/(II) mechanism or a redox-neutral Pd(II)-only mechanism can operate. In the latter pathway, C-C bond formation occurs through carbopalladation of the alkene, and C-O cleavage by β-carboxyl elimination. 1 Introduction 2 A Mechanistic Challenge: Activating Strong C-O Bonds 3 Exploiting Vinylogy for C-Cl and C-O Oxidative Additions 4 An Alternative Mechanism for Efficient Cross-Coupling Catalysis 5 Conclusions and Outlook.
Highly enantioselective and regioselective carbonyl reduction of cyclic α,β-unsaturated ketones using TarB-N02 and sodium borohydride
Kim, Jinsoo,Bruning, John,Park, Kevin E.,Lee, David J.,Singaram, Bakthan
supporting information; experimental part, p. 4358 - 4361 (2009/12/24)
Asymmetric 1,2-reduction of α,β-unsaturated ketones using TarB-NO2 and NaBH4 Is reported. Simple cycloalkenones give products In low enantiomeric excess. However, cycloalkenones with a-substituents, such as halides, alkyl, and aryl, have been enantioselectively reduced with this system to yield chiral allylic alcohols In enantiomeric excess up to 99%. The starting materials for TarB-N02 are inexpensive, and the boronlc acid can be easily recovered In high yield by a simple acid extraction.
VILSMEIER REAGENTS: PREPARATION OF β-HALO-α,β-UNSATURATED KETONES
Mewshaw, Richard E.
, p. 3753 - 3756 (2007/10/02)
A new method for the preparation of β-chloro and β-bromo-α,β-unsaturated ketones from β-diketones is described.Utilizing Vilsmeier reagents (prepared from N,N-dimethylformamide and oxalyl chloride or oxalyl bromide) β-halo-α,β-unsaturated ketones are isolated in excellent yields.
