54105-26-9

Upstream product

• 589-09-3 N-allyl-N-phenylamine 
• 201230-82-2 carbon monoxide 
• 156146-13-3 N-but-1-yn-4-yl-N-phenylamine 
• 623-26-7 terephthalonitrile 
• 4096-21-3 N-phenylpyrrolidine 
• 10602-08-1 2-ethynylbenzyl alcohol 
• 62-53-3 aniline 
• 4641-57-0 1-phenylpyrrolidin-2-one 
• 762-42-5 dimethyl acetylenedicarboxylate 

Relevant academic research and scientific papers

Photoredox Mediated Acceptorless Dehydrogenative Coupling of Saturated N-Heterocycles

We report herein a direct unsymmetric coupling and controllable aromatization reaction of saturated N-heterocycles enabled by synergistic photoredox and acid catalysis. The reaction furnishes C2-C3 connected biheterocycles in a highly chemo- and regiosele

Direct Arylation of α-Amino C(sp3)-H Bonds by Convergent Paired Electrolysis

A metal-free convergent paired electrolysis strategy to synthesize benzylic amines through direct arylation of tertiary amines and benzonitrile derivatives at room temperature has been developed. This TEMPO-mediated electrocatalytic reaction makes full use of both anodic oxidation and cathodic reduction without metals or stoichiometric oxidants, thus showing great potential and advantages for practical synthesis. This convergent paired electrolysis method provides a straightforward and powerful means to activate C?H bonds and realize cross-coupling with cathodically generated species.

The Divergent Cascade Reactions of Arylalkynols with Homopropargylic Amines or Electron-Deficient Olefins: Access to the Spiro-Isobenzofuran- b-pyrroloquinolines or Bridged-Isobenzofuran Polycycles

Two divergent cascade reactions of arylalkynols with homopropargylic amines or electron-deficient olefins were developed to synthesize the spiro-isobenzofuran-b-pyrroloquinolines or bridged-isobenzofuran heterocycles in good yields, respectively. One reaction actually involved intramolecular 5-endo-dig hydroamination cyclization-protonation of homopropargylic amines to give cycloiminium ions and intramolecular 5-exo-dig hydroalkoxylation cyclization of arylalkynols to generate isobenzofuran with exocyclic double bond, followed by the nontypical Povarov-type reaction in the presence of PtCl2/FeCl3 cocatalysts. The other underwent intramolecular hydroalkoxylation cycloisomerization of alkynols with the subsequent normal [4 + 2] cycoaddition with dienophiles. Herein, the arylalkynols acted as both "masked" electron-rich olefins and "masked" electron-rich dienes.

Dual C(sp3)?H Bond Functionalization of N-Heterocycles through Sequential Visible-Light Photocatalyzed Dehydrogenation/[2+2] Cycloaddition Reactions

Herein we describe a mild method for the dual C(sp3)?H bond functionalization of saturated nitrogen-containing heterocycles through a sequential visible-light photocatalyzed dehydrogenation/[2+2] cycloaddition procedure. As a complementary approach to the well-established use of iminium ion and α-amino radical intermediates, the elusive cyclic enamine intermediates were effectively generated by photoredox catalysis under mild conditions and efficiently captured by acetylene esters to form a wide array of bicyclic amino acid derivatives, thus enabling the simultaneous functionalization of two vicinal C(sp3)?H bonds.

Synthesis of α-Formylated N-Heterocycles and Their 1,1-Diacetates from Inactivated Cyclic Amines Involving an Oxidative Ring Contraction

A novel synthesis of pyrrolidine-2-carbaldehydes or tetrahydropyridine-2-carbaldehydes from the cascade reactions of N-arylpiperidines or N-arylazepanes is presented. Mechanistically, the formation of the title compounds involves an unprecedented oxidative ring contraction of inactivated cyclic amines via Cu(OAc)2/KI/O2-promoted oxidative cleavage and reformation of the C-N bond. Interestingly, when PhI(OAc)2 was used in place of KI, 1,1-diacetates of the corresponding aldehydes were directly obtained with good efficiency. To the best of our knowledge, this is the first example of regioselective C(sp3)-H bond functionalization and C(sp3)-N bond activation of saturated cyclic amines using copper salt and oxygen.

Visible-Light-Promoted Asymmetric Cross-Dehydrogenative Coupling of Tertiary Amines to Ketones by Synergistic Multiple Catalysis

Reported herein is an unprecedented photocatalytic asymmetric cross-dehydrogenative coupling reaction between tertiary amines and simple ketones, and it proceeds by synergistic multiple catalysis with substoichiometric amounts of a hydrogen acceptor. This process is enabled by a simple chiral primary amine catalyst through the coupling of a catalytic enamine intermediate and an iminium cation intermediate in situ generated from tetrahydroisoquinoline derivatives by coupled Ru/Co catalysis.

Counteranion-Controlled Unprecedented Diastereo- and Enantioselective Tandem Formal Povarov Reaction for Construction of Bioactive Octahydro-Dipyrroloquinolines

The asymmetric inverse-electron-demand hetero-Diels-Alder (IEHDA) reactions of imines and dienophiles have emerged as an attractive tool for derivatizing optically active complex azaheterocycles. In comparison, such reactions involving iminium ions remain great challenges because of low association of iminium ions with neutral catalytic centers. To overcome this, we report a metal-phosphate-catalyzed asymmetric tandem hydroamination/formal Povarov reaction of secondary aminoalkynes via a chiral counteranion-controlled iminium ion intermediate strategy. Critical to the success of this challenging strategy was chiral phosphate as an ion pair to achieve counteranion-controlled asymmetric reaction of in situ-generated iminium ions. This method enables a convenient, powerful, and atom-economical access to tetracyclic octahydro-dipyrroloquinoline frameworks bearing multiple contiguous stereogenic centers in good yields with diastereo- and enantioselectivities, from acyclic starting materials, and the catalyst loadings could be as low as 1 mol %. The asymmetric cross-coupling reaction of different aminoalkynes has further been demonstrated with good results. Furthermore, this methodology was applied to enantioselective synthesis of incargranine B aglycone epimer in only two steps. The reaction is demonstrated to proceed through a stepwise process for formal Povarov reaction.

The Stereochemistry of Organometallic Compounds. XL. Rhodium-Catalysed Reactions of Hydrogen and Carbon Monoxide with Alkenylanilines

Rhodium-catalysed reactions of o- or p-cyano-N-allylanilines with H2/CO give N-arylpyrrolidine aldehydes resulting from a double hydroformylation sequence.In contrast reactions of o- or p-methyl-N-allylanilines or N-allylaniline itself with H2/CO give 'dimeric' compounds resulting from self-condensation reactions of an initially formed hydroformylation product together with varying amounts of the double hydroformylation product.Similar reactions of o-cyano-N-but-3-enylanilines give low yields of double hydroformylation products and major products arising from hydrogenation or cross coupling of intermediate enamines.The structure of one of these products, N-2-cyanophenyl-5-(N'-2-cyanophenyl-3-methylpyrrolidin-2-yl)-1,2,3,4-tetrahydropyridine (17) (IUPAC name: 2--1,2,3,4-tetrahydropyridin-1-yl>benzonitrile) was confirmed by an X-ray single-crystal structure determination.