872884-40-7

Upstream product

• 872884-20-3 (Z)-allyl (1-phenylprop-1-en-1-yl) carbonate 
• 93-55-0 1-phenyl-propan-1-one 
• 123-54-6 acetylacetone 
• 108-59-8 malonic acid dimethyl ester 
• 2004-70-8 1-methylbuta-1,3-diene 
• 100-52-7 benzaldehyde 
• 15022-08-9 diallylcarbonate 
• 94287-27-1 tert-butyldimethyl((1-phenylprop-1-en-1-yl)oxy)silane 
• 37471-46-8 1-phenyl-1-trimethylsiloxypropene 
• 883901-67-5 allyl 2-methyl-3-oxo-3-phenylpropanoate 
• 883901-71-1 C₁₃H₁₄O₃ 
• 66323-99-7 trimethyl[(Z)-(1-phenyl-1-propenyl)oxy]silane 
• 591-87-7 Allyl acetate 

Downstream Products

• 872884-41-8 (S)-(+)-2-methyl-1-phenylpentan-1-one 

Relevant academic research and scientific papers

α- And β-Functionalized Ketones from 1,3-Dienes and Aldehydes: Control of Regio- And Enantioselectivity in Hydroacylation of 1,3-Dienes

Ketones are among the most widely used intermediates in organic synthesis, and their synthesis from inexpensive feedstocks could be quite impactful. Regio- and enantioselective hydroacylation reactions of dienes provide facile entry into useful ketone-bearing chiral motifs with an additional latent functionality (alkene) suitable for further elaboration. Three classes of dienes, 2- or 4-monosubstituted and 2,4-disubstituted 1,3-dienes, undergo cobalt(I)-catalyzed regio- and enantioselective hydroacylation, giving products with high enantiomeric ratios (er). These reactions are highly dependent on the ligands, and we have identified the most useful ligands and reaction conditions for each class of dienes. 2-Substituted and 2,4-disubstituted dienes predominantly undergo 1,2-addition, whereas 4-substituted terminal dienes give highly enantioselective 4,1- or 4,3-hydroacylation depending on the aldehyde, aliphatic aldehydes giving 4,1-addition and aromatic aldehydes giving 4,3-addition. Included among the substrates are feedstock dienes, isoprene (US$1.4/kg) and myrcene (US$129/kg), and several common aldehydes. We propose an oxidative dimerization mechanism that involves a Co(I)/Co(III) redox cycle that appears to be initiated by a cationic Co(I) intermediate. Studies of reactions using isolated neutral and cationic Co(I) complexes confirm the critical role of the cationic intermediates in these reactions. Enantioselective 1,2-hydroacylation of 2-trimethylsiloxy-1,3-diene reveals a hitherto undisclosed route to chiral siloxy-protected aldols. Finally, facile syntheses of the anti-inflammatory drug (S)-Flobufen (2 steps, 92% yield, >99:1 er) and the food additive (S)-Dihydrotagetone (1 step, 83% yield; 96:4 er) from isoprene illustrate the power of this method for the preparation of commercially relevant compounds.

Construction of tertiary chiral centers by Pd-catalyzed asymmetric allylic alkylation of prochiral enolate equivalents

Abstract The palladium-catalyzed decarboxylative allylic alkylation of enol carbonates derived from lactams and ketones is described. Employing these substrates with an electronically tuned Pd catalyst system trisubstituted chiral centers are produced. These stereocenters have been previously challenging to achieve using Pd complex/chiral P-N ligand systems.

Investigation of a novel diamine based chiral auxiliary in the asymmetric alkylation of ketones

A novel chiral auxiliary containing a pyrrolidine ring has been utilised in the preparation of various chiral ketones with good to excellent enantioselectivities (up to 92%). It has been successfully employed in aldol and Michael reactions giving moderate to high selectivity.

Enantioselective decarboxylative alkylation reactions: Catalyst development, substrate scope, and mechanistic studies

α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center. Sly as a PHOX: The development of an enantioselective decarboxylative palladium-catalyzed allylic alkylation reaction, utilizing phosphinooxazoline ligands, is described. The catalyst is applied to a range of allyl enol carbonate, silyl enol ether, and allyl β-ketoester substrates to provide alkylated ketone products in excellent yield and good ee (see scheme). The utility of these products is demonstrated by their use in several asymmetric syntheses. Mechanistic studies are reported suggesting an unusual inner-sphere mechanism. Copyright

Palladium-catalyzed decarboxylative asymmetric allylic alkylation of enol carbonates

Palladium-catalyzed decarboxylative asymmetric allylic alkylation (DAAA) of allyl enol carbonates as a highly chemo-, regio-, and enantioselective process for the synthesis of ketones bearing either a quaternary or a tertiary R-stereogenic center has been investigated in detail. Chiral ligand L4 was found to be optimal in the DAAA of a broad scope of cyclic and acyclic ketones including simple aliphatic ketones with more than one enolizable proton. The allyl moiety of the carbonates has been extended to a variety of cyclic or acyclic disubstituted allyl groups. Our mechanistic studies reveal that, similar to the direct allylation of lithium enolates, the DAAA reaction proceeds through an "outer sphere" S N2 type of attack on the π-allylpalladium complex by the enolate. An important difference between the DAAA reaction and the direct allylation of lithium enolates is that in the DAAA reaction, the nucleophile and the electrophile were generated simultaneously. Since the π-allylpalladium cation must serve as the counterion for the enolate, the enolate probably exists as a tight-ion-pair. This largely prevents the common side reactions of enolates associated with the equilibrium between different enolates. The much milder reaction conditions as well as the much broader substrate scope also represent the advantages of the DAAA reaction over the direct allylation of preformed metal enolates.

Enantioselective, catalytic allylation of ketones and olefins

Compounds containing a substituted or unsubstituted allyl group directly bound to a chiral carbon atom are prepared enantioselectively. Starting reactants are either chiral or achiral, and may or may not contain an attached allyloxycarbonyl group as a sub

Palladium-catalyzed asymmetric allylic α-alkylation of acyclic ketones

The first example of Pd-catalyzed asymmetric allyl alkylation of the conformationally nonrigid acyclic ketone enolates is reported with excellent yields, regioselectivity, and enantioselectivity. The double bond geometry of the allyl enol carbonates affec

Highly enantioselective Pd-catalyzed allylic alkylations of acyclic ketones

(Chemical Equation Presented) Pocket the difference: Highly enantioselective allylic alkylation of simple acyclic ketones is carried out by using a Pd catalyst with a "chiral pocket" ligand 1 (see scheme). The addition of a Lewis acid such as AgBr and the