812639-01-3

Upstream product

• 63934-48-5 allyl cyanoformate 
• 2408-37-9 2,2,6-trimethylcyclohexan-1-one 
• 2816-57-1 2,6-dimethylcyclohexanone 
• 2937-50-0 Allyl chloroformate 

Downstream Products

• 1322705-85-0 C₂₂H₂₈O₃ 
• 1322705-96-3 C₂₂H₂₇BrO₃ 
• 1322706-04-6 C₂₃H₃₃BrO₃ 
• 1322706-02-4 C₂₃H₃₁BrO₃ 
• 1322706-00-2 C₂₂H₂₉BrO₃ 
• 1322705-98-5 C₂₂H₂₉BrO₃ 
• 1322705-84-9 C₂₂H₂₇BrO₃ 

Relevant academic research and scientific papers

Formal total syntheses of classic natural product target molecules via palladium-catalyzed enantioselective alkylation

Pd-catalyzed enantioselective alkylation in conjunction with further synthetic elaboration enables the formal total syntheses of a number of "classic" natural product target molecules. This publication highlights recent methods for setting quaternary and tetrasubstituted tertiary carbon stereocenters to address the synthetic hurdles encountered over many decades across multiple compound classes spanning carbohydrate derivatives, terpenes, and alkaloids. These enantioselective methods will impact both academic and industrial settings, where the synthesis of stereogenic quaternary carbons is a continuing challenge.

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

The catalytic enantioselective, protecting group-free total synthesis of (+)-dichroanone

Herein we report the first enantioselective total synthesis of (+)-dichroanone, confirming the absolute configuration of the natural product. This protecting group-free route features the first application of our enantioselective Tsuji allylation in the context of a natural product total synthesis. Additionally, this 11-step preparation of the molecule from commercial material features a novel Kumada-aromatization strategy and a rapid sequence for the conversion of a phenol to a hydroxy-p-benzoquinone. Copyright

Deracemization of quaternary stereocenters by Pd-catalyzed enantioconvergent decarboxylative allylation of racemic β-ketoesters

(Chemical Equation Presented) Stereochemical alchemy! Racemic allyl β-ketoesters allow the regiocontrolled formation of enolates, where the same catalyst is intimately involved in both the stereoablative (C-C bond-breaking) and stereoselective (C-C bond-f

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