1332344-13-4

Upstream product

• 100-52-7 benzaldehyde 
• 104-94-9 4-methoxy-aniline 
• 260967-14-4 benzyl N-[(1E)-prop-1-en-1-yl]-carbamate 
• 1078123-69-9 benzyl (E/Z)-prop-1-enylcarbamate 
• 1613-90-7 4-methoxy-N-[(E)-phenylmethylidene]aniline 
• 783-08-4 [4-(benzylideneamino)phenyl]methanol 
• 100-17-4 para-methoxynitrobenzene 
• 4546-20-7 p-methoxyphenylhydroxylamine 
• 19064-76-7 N-benzylidene-4-methoxyaniline oxide 
• 1137-96-8 N-(benzylidene)aniline N-oxide 

Relevant academic research and scientific papers

Enantioselective synthesis and selective functionalization of 4-aminotetrahydroquinolines as novel GLP-1 secretagogues

Polysubstituted tetrahydroquinolines were obtained in moderate to high yields (28% to 92%) and enantiomeric ratios (er 89:11 to 99:1) by a three-component Povarov reaction using a chiral phosphoric acid catalyst. Significantly, post-Povarov functional group interconversions allowed a rapid access to a library of 36 enantioenriched 4-aminotetrahydroquinoline derivatives featuring five points of diversity. Selected analogs were assayed for their ability to function as glucagon-like peptide-1 (GLP-1) secretagogues.

Tandem Chiral Cu(II) Phosphate-Catalyzed Deoxygenation of Nitrones/Enantioselective Povarov Reaction with Enecarbamates

A new catalytic enantioselective tandem deoxygenation/aza-Diels-Alder reaction of nitrones with enecarbamates was serendipitously discovered in the presence of chiral copper(II) diphosphate complexes. This process affords a wide range of 4-aminotetrahydroquinolines in respectable yields under mild conditions with good to excellent ee values.

Enantioselective and Regiodivergent Functionalization of N-Allylcarbamates by Mechanistically Divergent Multicatalysis

A pair of mechanistically divergent multicatalytic reaction sequences has been developed consisting of nickel-catalyzed isomerization of N-allylcarbamates and subsequent phosphoric-acid-catalyzed enantioselective functionalization of the resulting intermediates. By appropriate selection of reaction partners, in situ generated imines and ene-carbamates are mechanistically partitioned to yield opposing functionalized products. Formal α-functionalization to give protected α-arylamines is achieved upon enantioselective Friedel–Crafts reaction with arene nucleophiles, whereas formal β-functionalization is achieved upon reaction with diarylimine electrophiles in an enantioselective Povarov-[4+2] cycloaddition.

Chiral phosphoric acid-catalyzed enantioselective three-component Povarov reaction using enecarbamates as dienophiles: Highly diastereo- and enantioselective synthesis of substituted 4-aminotetrahydroquinolines

A chiral phosphoric acid (5)-catalyzed three-component Povarov reaction of aldehydes 2, anilines 3, and enecarbamates 4 afforded cis-4-amino-2-aryl(alkyl)- 1,2,3,4-tetrahydroquinolines 1 in high yields with excellent diastereoselectivities (>95%) and almost complete enantioselectivities (up to >99% ee). The reaction was applicable to a wide range of anilines bearing electron-donating (OMe) and electron-withdrawing groups (e.g., Cl, CF 3, NO2) and allowed, for the first time, aliphatic aldehydes to be employed in the enantioselective Povarov reaction. With β-substituted acyclic enecarbamates, 2,3,4-trisubstituted 1,2,3,4-tetrahydroquinolines with three contiguous stereogenic centers were produced in excellent diastereo- and enantioselectivities (87 to >99% ee). A detailed study of the active catalytic species allowed us to reduce the catalyst loading from 10% to 0.5% with no deterioration of enantiomeric excess. In addition, mechanistic studies allowed us to conclude unequivocally that the Povarov reaction involving enecarbamate as dienophile proceeded via a stepwise mechanism. The key role of the free NH function of the enecarbamate in the success of this transformation was demonstrated. NMR experiments indicating the catalyst-substrate interaction as well as a linear correlation between catalyst and product ee's were also documented.