90838-76-9

Upstream product

• 55282-88-7 1-deuteriocyclohex-2-en-1-ol 
• 960-16-7 tributylphenylstannane 
• 203798-11-2 1-deuteriocyclohex-2-en-1-yl acetate 
• 28557-00-8 phenylzinc chloride 
• 930-68-7 cyclohexenone 
• 1309466-64-5 C₁₂H₂₂⁽²⁾HO₃PS 
• 100-58-3 phenylmagnesium bromide 
• 1309466-84-9 C₈H₁₁⁽²⁾HOS 
• 102853-26-9 α-deuterio-2-cyclohexenyl mesitoate 

Relevant academic research and scientific papers

Cu(I)-catalyzed, α-selective, allylic alkylation reactions between phosphorothioate esters and organomagnesium reagents

Regiocontrol of allylic alkylation reactions involving hard nucleophiles remains a significant challenge and continues to be an active area of research. The lack of general methods in which α-alkylation is favored underscores the need for the development of new processes for achieving this type of selectivity. We report that Cu(I) catalyzes the allylic substitution of phosphorothioate esters with excellent α-regioselectivity, regardless of the nature of the Grignard reagent that is used. To the best of our knowledge, the Cu-catalyzed allylic alkylation of phosphorothioate esters has never been described. We have also developed a simple protocol for inducing high α selectivity starting from secondary allylic halides. This is accomplished by using sodium phosphorothioates as an additive.

Alkylation of Allylic Derivatives. 11. Copper(I)-Catalyzed Cross Coupling of Allylic Carboxylates with Grignard Reagents

Reactions of allylic carboxylates with Grignard reagents containing catalytic amounts (1-10 mol percent) of cuprous salts give high yields of cross-coupled products.With alkyl Grignard reagents, regiochemistry can be controlled by choice of cuprous salt.With cuprous halides, little regiospecificity is observed.There is a small excess of γ-coupling in unbiased systems such as 5-methyl-2-cyclohexenyl (1), 2-cyclohexenyl (3), and β-phenylallyl (5) carboxylates.With CuCN, complete regiospecificity (exclusive γ-coupling) is observed with all alkyl Grignard reagents in unbiased systems, and with n-butylmagnesium halide >97percent γ-coupling results with α-methyl-γ-phenylallyl pivalate (7-OPiv) which is biased in favour of coupling at the α-position.In sharp contrast to alkyl Grignard reagents, phenyl and vinyl Grignard reagents containing CuCN show no regiospecificity.

PALLADIUM-CATALYZED ASYMMETRIC COUPLING REACTIONS BETWEEN ALLYLIC ACETATES AND ORGANOZINC REAGENTS. MECHANISTIC IMPLICATIONS

Asymmetric induction and deuterium distribution studies have provided information about the mechanism of the palladium-catalyzed coupling reaction between allylic acetates and phenylzinc chloride, namely the presence of a symmetric η3-allylic ligand in the inetrmediate, probably along with a monodentate phosphine ligand.

PALLADIUM-CATALYZED CROSS COUPLING OF ALLYL HALIDES WITH ORGANOTIN REAGENTS: A METHOD OF JOINING HIGHLY FUNCTIONALIZED PARTNERS REGIOSELECTIVELY AND STEREOSPECIFICALLY.

The palladium-catalyzed reaction of allyl halides with aryl- and vinyltin reagents gives high yields of cross-coupled products. In the presence of 1-3 atm of carbon monoxide, ketones are obtained, resulting from cross coupling accompanied by carbon monoxide insertion. The reaction is mild and tolerant of a wide variety of functionalities (OH, OR, CN, CO//2R, CHO) on either the allyl chloride or the tin reagent. Coupling at the allyl halide partner proceeds with inversion of configuration at the carbon bearing the halide, with retention of geometry at the allylic double bond, and with a regioselectivity for the least-substituted carbon in the allylic framework. Retention of double-bond geometry is observed in the vinyltin partner.