86950-89-2

Upstream product

• 583-60-8 2-Methylcyclohexanone 
• 2937-50-0 Allyl chloroformate 
• 7770-41-4 1-methyl-2-oxocyclohexanecarboxylic acid 2-propenyl ester 

Downstream Products

• 1121-18-2 2-methyl-2-cyclohexen-1-one 
• 16178-87-3 2-methyl-2-allylcyclohexanone 
• 583-60-8 2-Methylcyclohexanone 
• 94-66-6 2-allylcyclohexan-1-one 
• 812639-07-9 (2S)-2-methyl-2-(2-propen-1-yl)cyclohexanone 
• 812639-20-6 C₁₂H₁₈O₂ 
• 4087-39-2 (S)-(+)-4,4a,5,6,7,8-hexahydro-4a-methyl-2(3H)-naphthalenone 
• 91306-29-5 (S)-2-methyl-2-(3-oxobutyl)-cyclohexanone 
• 54725-16-5 Δ³⁽¹⁾-8-Methyl-hydrindenon-(2) 
• 812639-24-0 4-((S)-6-Methyl-1,4-dioxa-spiro[4.5]dec-6-yl)-butan-2-one 
• 275825-05-3 (S)-2-methyl-2-(4-methylpent-4-en-1-yl)cyclohexanone 

Relevant academic research and scientific papers

CERTAIN PLADIENOLIDE COMPOUNDS AND METHODS OF USE

The present disclosure provides novel pladienolide compounds, pharmaceutical compositions containing such compounds, and methods for using the compounds as therapeutic agents. These compounds may be useful in the treatment of cancers, particularly cancers in which agents that target the spliceosome and mutations therein are known to be useful. Also provided herein are methods of treating cancers by administering at least one compound disclosed herein and at least one additional therapy.

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.

The inner-sphere process in the enantioselective Tsuji allylation reaction with (S)-t-Bu-phosphinooxazoline liqands

We propose an inner-sphere mechanism explaining the unique performance of the Tsuji asymmetrical allylation reaction using hard prochiral enolate nucleophiles and non-prochiral allyl groups. Using first principles quantum mechanics (B3LYP density function

The enantioselective Tsuji allylation

The first catalytic enantioselective examples of the Tsuji allylation using enol carbonates and enol silanes are described. The products possess a quaternary stereogenic center and are useful building blocks for synthetic chemistry. Copyright

SYNTHESIS OF γ,δ-UNSATURATED KETONES BY THE INTRAMOLECULAR DECARBOXYLATIVE ALLYLATION OF ALLYL β-KETO CARBOXYLATES AND ALKENYL ALLYL CARBONATES CATALYZED BY MOLYBDENUM, NICKEL, AND RHODIUM COMPLEXES

Allyl β-keto carboxylates and alkenyl allyl carbonates were converted to γ,δ-unsaturated ketones by the intramolecular decarboxylative allylation catalyzed by molybdenum, nickel, and rhodium complexes.

PALLADIUM-CATALYZED ALLYLATION OF KETONES AND ALDEHYDES VIA ALLYL ENOL CARBONATES

Rearrangement of allyl enol carbonates, prepared from ketones or aldehydes by trapping their enolates with allyl chloroformate, to give α-allyl ketones or aldehydes regioselectively is catalyzed by palladium-phosphine complexes under mild conditions.