724767-54-8

Upstream product

• 1116-98-9 cyanoacetic acid tert-butyl ester 
• 794-94-5 p-Methoxybenzoic anhydride 
• 1236004-44-6 tert-butyl α-cyano-α-diazoacetate 
• 100-66-3 methoxybenzene 
• 24424-99-5 di-tert-butyl dicarbonate 
• 104-47-2 p-methoxybenzylnitrile 

Downstream Products

• 1010433-78-9 C₁₈H₂₃N₃O₇ 
• 1258222-63-7 3-tert-butyl 1,2-dimethyl (1Z,3S)-3-cyano-3-(4-methoxyphenyl)prop-1-ene-1,2,3-tricarboxylate 

Relevant academic research and scientific papers

Catalytic, Asymmetric Dearomative Synthesis of Complex Cyclohexanes via a Highly Regio- And Stereoselective Arene Cyclopropanation Using α-Cyanodiazoacetates

Arene cyclopropanation offers a direct route to higher-order, non-aromatic carbocycles; however, the inherent issue of dictating site selectivity has cumbered the development of novel intermolecular reactions that directly engage the arene pool. This paper describes a highly regio- and stereoselective, Rh2[(S)-PTTL]4-catalyzed arene cyclopropanation using α-cyanodiazoacetates to afford stable norcaradienes bearing three stereogenic centers, one of which is an all-carbon quaternary center. The enantioenriched norcaradienes served as tunable templates for further transformation into stereochemically dense, fused and bicyclic carbocycles containing transmutable functionality.

Enantioselective construction of tetrasubstituted stereogenic carbons through bronsted base catalyzed michael reactions: α′-hydroxy enones as key enoate equivalent

Catalytic and asymmetric Michael reactions constitute very powerful tools for the construction of new C-C bonds in synthesis, but most of the reports claiming high selectivity are limited to some specific combinations of nucleophile/electrophile compound types, and only few successful methods deal with the generation of all-carbon quaternary stereocenters. A contribution to solve this gap is presented here based on chiral bifunctional Bronsted base (BB) catalysis and the use of α′-oxy enones as enabling Michael acceptors with ambivalent H-bond acceptor/donor character, a yet unreported design element for bidentate enoate equivalents. It is found that the Michael addition of a range of enolizable carbonyl compounds that have previously demonstrated challenging (i.e., α-substituted 2-oxindoles, cyanoesters, oxazolones, thiazolones, and azlactones) to α′-oxy enones can afford the corresponding tetrasubstituted carbon stereocenters in high diastereo- and enantioselectivity in the presence of standard BB catalysts. Experiments show that the α′-oxy ketone moiety plays a key role in the above realizations, as parallel reactions under identical conditions but using the parent α,β-unsaturated ketones or esters instead proceed sluggish and/or with poor stereoselectivity. A series of trivial chemical manipulations of the ketol moiety in adducts can produce the corresponding carboxy, aldehyde, and ketone compounds under very mild conditions, giving access to a variety of enantioenriched densely functionalized building blocks containing a fully substituted carbon stereocenter. A computational investigation to rationalize the mode of substrate activation and the reaction stereochemistry is also provided, and the proposed models are compared with related systems in the literature.

Mechanistic consideration of asymmetric CN and CC bond formations with bifunctional chiral ir and ru catalysts

The mechanism of two enantioselective reactions, direct amination of α-cyanoacetates 3 with azodicarboxylates 4 and CC bond formation reaction of α-cyanoacetates with acetylenic esters 6, catalyzed by chiral bifunctional Ir and Ru complexes, Cp*Ir[(S,S)-N

Enantioselective direct amination of α-cyanoacetates catalyzed by bifunctional chiral Ru and Ir amido complexes

The bifunctional chiral amido Ir complex catalyzed asymmetric electrophilic direct amination of α-substituted α-cyanoacetates using azodicarboxylates proceeds rapidly to provide the corresponding hydrazine adducts in high yields and with excellent ee values. Copyright