67679-06-5

Upstream product

• 591-87-7 Allyl acetate 
• 130203-11-1 (S)-2-[(Diphenylphosphanyl)-methyl]-1-((Z)-2-phenyl-propenyl)-pyrrolidine 
• 130203-10-0 allyl o-toluenesulfonate 
• 128402-81-3 (S)-3-Methyl-2-[2-phenyl-prop-(E)-ylideneamino]-butyric acid allyl ester 
• 106-95-6 allyl bromide 
• 24401-39-6 2-methyl-2-phenyl-pentenal 
• 33215-90-6 isopropyl-(2-phenyl-propylidene)-amine 
• 6728-21-8 allyl mesylate 
• 34713-70-7 2-Phenylpropanal 
• 88224-01-5 L-valine allyl ester 
• 15784-26-6 allyl t-butyl carbonate 
• 1342313-03-4 (R)-2-methyl-2-phenyl-4-(1-phenyl-1H-tetrazol-5-ylsulfonyl)butanal 
• 107-18-6 allyl alcohol 
• 135055-75-3 (S)-(-)-N-tert-butoxycarbonyl-2-<(diphenylphosphino)methyl>pyrrolidine 

Relevant academic research and scientific papers

Nickel/Enamine Cooperative Catalysis Enables Highly Enantioselective Allylic Alkylation of α-Branched Aldehydes

All-carbon quaternary stereocenters constitute a significant portion of natural products and bioactive compounds. Here we disclose a nickel and chiral amine cooperative catalysis to enable a highly enantioselective allylic alkylation reaction between α-branched aldehydes and a wide scope of allyl esters, allowing the all-carbon quaternary stereocenter to be accessed with excellent enantioselectivity (up to 98% ee) and structural diversity. The general synthetic applicability has been showcased by the enantioselective synthesis of key chiral building blocks to access (+)-eptazocine, (?)-aphanorphine, and other two bioactive compounds.

Organocatalytic Asymmetric α-Allylation and Propargylation of α-Branched Aldehydes with Alkyl Halides

Enantioselective α-allylation and -propargylation of α-branched aldehydes with alkyl halides was successfully performed using a chiral primary amino acid organocatalyst. This alkylation reaction, involving the generation of a chiral quaternary carbon stereocenter, proceeded smoothly in a mildly basic aqueous solution of potassium hydrogen carbonate to furnish α-allylated or -propargylated aldehydes in a good yield (up to 87%) and high enantioselectivity (up to 96% ee).

Counterion-Enhanced Pd/Enamine Catalysis: Direct Asymmetric α-Allylation of Aldehydes with Allylic Alcohols by Chiral Amines and Achiral or Racemic Phosphoric Acids

We report a straightforward and efficient Pd/enamine catalytic procedure for the direct asymmetric α-allylation of branched aldehydes. The use of simple chiral amines and easily prepared achiral or racemic phosphoric acids, together with a suitable Pd-source resulted in a highly active and enantioselective catalyst system for the allylation of various α-branched aldehydes with different allylic alcohols. The reported procedure could provide an easy access to both product antipodes. Furthermore, two possible orthogonal derivatizations of the enantioenriched aldehydes were performed without any decrease in enantioselectivity.

Enantioselective rhodium-catalyzed allylic substitution with a nitrile anion:construction of acyclic quaternary carbon stereogenic centers

A direct and highly enantioselective rhodium-catalyzed allylic alkylation of allyl benzoate with α-substituted benzyl nitrile pronucleophiles is described. This simple protocol provides a new approach toward the synthesis of acyclic quaternary carbon stereogenic centers and provides the first example of the direct asymmetric alkylation of a nitrile anion. The synthetic utility of the nitrile products is amply demonstrated through conversion to various functional groups and the synthesis of a bioactive aryl piperazine in an expeditious four-step sequence.

Asymmetric α-allylation of α-branched aldehydes with allyl alcohols by synergistic catalysis using an achiral palladium complex and a chiral primary amino acid

Highly enantioselective direct α-allylation of α-branched aldehydes with simple allyl alcohols was achieved by the combined use of an achiral transition-metal catalysis with a palladium complex and a chiral organocatalysis with a readily obtainable primary α-amino acid. Various α-allylated aldehydes possessing a stereocontrolled quaternary carbon stereogenic center were synthesized in high yields with high enantioselectivity. Georg Thieme Verlag Stuttgart New York.

Direct asymmetric α-allylation of α-branched aldehydes by two catalytic systems with an achiral Pd complex and a chiral primary α-amino acid

Direct α-allylation of α-branched aldehydes was successfully carried out with a readily available allyl ester by combined use of two catalytic systems: Tsuji-Trost allylation reaction with an achiral palladium complex and enamine catalysis with a chiral primary α-amino acid. A quaternary carbon stereogenic center was constructed stereoselectively to give various 2,2-disubstituted pent-4-enals in good yields with high enantioselectivity.

Direct asymmetric α-allylation of aldehydes with simple allylic alcohols enabled by the concerted action of three different catalysts

Triple catalysis: The title reaction between α-branched aldehydes and allylic alcohols, which generates all-carbon quaternary stereogenic centers, constitutes the first asymmetric Tsuji-Trost-type α-allylation of carbonyl compounds with allylic alcohol (s

Enantioselective organocatalytic formal allylation of α-branched aldehydes

Heteroarylvinyl sulfone 1 has been successfully used as a new sulfonyl Michael acceptor in aminocatalytic reactions with branched aldehydes. Subsequent one-pot Julia-Kocienski olefination allows the challenging preparation of enantiomerically pure α-allylated aldehydes bearing C-α quaternary carbons.

The palladium-catalyzed asymmetric α-allylations of carbonyl compounds with chiral allyl esters via enamines and imines

A novel and excellent method for asymmetric α-allylation of carbonyl compounds via their chiral enamines or imines bearing allyl esters has been developed. Readily available chiral allyl esters having chirality at the α- position of the ester carbonyl group, such as (S)-proline and other (S)-α- amino acid allyl esters, have been found to serve as good asymmetric allylating reagents in palladium-catalyzed reactions of the chiral enamines and imines derived from them. The use of (S)-proline or (S)-valine allyl esters as the amino parts in the enamines or imines provided the highest optical yields of the corresponding α-allyl carbonyl compounds. A mechanism for asymmetric induction is proposed based on the stereochemical results obtained.

The Palladium-catalyzed Asymmetric Allylations of Chiral Hydrazones Bearing Phosphine Groups. Stereoelectronic Effects of Allylating Reagents on Asymmetric Induction

The palladium-catalyzed allylations of chiral hydrazones bearing phosphine groups were executed successfully under neutral reaction conditions with various allylating reagents, affording optically active α-allyl carbonyl compounds.The systematic and stere