120347-89-9

Upstream product

• 699-98-9 Pyridine-2,3-dicarboxylic anhydride 
• 100-46-9 benzylamine 
• 4664-00-0 2,3-pyridinedicarboximide 
• 18184-75-3 6-benzyl-5H-pyrrolo[3,4-b]pyridine-5,7(6H)-dione 
• 89-00-9 Pyridine-2,3-dicarboxylic acid 

Downstream Products

• 100870-26-6 N-Benzyl-2-hydroxymethyl-nicotinamide 
• 1177391-82-0 7-(acetylmethyl)-6-benzyl-6,7-dihydro-5H-pyrrolo[3,4-b]pyridin-5-one 
• 1177391-80-8 7-(benzoylmethyl)-6-benzyl-6,7-dihydro-5H-pyrrolo[3,4-b]pyridin-5-one 
• 5657-51-2 7H-furo[3,4-b]pyridin-5-one 

Relevant academic research and scientific papers

Electroselective and Controlled Reduction of Cyclic Imides to Hydroxylactams and Lactams

An efficient and practical electrochemical method for selective reduction of cyclic imides has been developed using a simple undivided cell with carbon electrodes at room temperature. The reaction provides a useful strategy for the rapid synthesis of hydroxylactams and lactams in a controllable manner, which is tuned by electric current and reaction time, and exhibits broad substrate scope and high functional group tolerance even to reduction-sensitive moieties. Initial mechanistic studies suggest that the approach heavily relies on the utilization of amines (e.g., i-Pr2NH), which are able to generate α-aminoalkyl radicals. This protocol provides an efficient route for the cleavage of C-O bonds under mild conditions with high chemoselectivity.

Chemoselective Electrosynthesis Using Rapid Alternating Polarity

Challenges in the selective manipulation of functional groups (chemoselectivity) in organic synthesis have historically been overcome either by using reagents/catalysts that tunably interact with a substrate or through modification to shield undesired sites of reactivity (protecting groups). Although electrochemistry offers precise redox control to achieve unique chemoselectivity, this approach often becomes challenging in the presence of multiple redox-active functionalities. Historically, electrosynthesis has been performed almost solely by using direct current (DC). In contrast, applying alternating current (AC) has been known to change reaction outcomes considerably on an analytical scale but has rarely been strategically exploited for use in complex preparative organic synthesis. Here we show how a square waveform employed to deliver electric current - rapid alternating polarity (rAP) - enables control over reaction outcomes in the chemoselective reduction of carbonyl compounds, one of the most widely used reaction manifolds. The reactivity observed cannot be recapitulated using DC electrolysis or chemical reagents. The synthetic value brought by this new method for controlling chemoselectivity is vividly demonstrated in the context of classical reactivity problems such as chiral auxiliary removal and cutting-edge medicinal chemistry topics such as the synthesis of PROTACs.

Alkoxide-Catalyzed Hydrosilylation of Cyclic Imides to Isoquinolines via Tandem Reduction and Rearrangement

An alkoxide-catalyzed hydrosilylation of cyclic imides to isoquinolines was realized via tandem reduction and rearrangement. Using TMSOK as the catalyst and (EtO)2MeSiH as the reductant, a series of cyclic imides containing different functional groups were reduced to the corresponding 3-aryl isoquinolines in moderate to good yields. The scenario of the reaction pathway was supposed to involve the reduction of imides to ω-hydroxylactams, which underwent rearrangement in the presence of a base catalyst, and then the carbonyl reduction, followed by siloxy elimination.

Potassium Hydroxide-Catalyzed Chemoselective Reduction of Cyclic Imides with Hydrosilanes: Synthesis of ω-Hydroxylactams and Lactams

Potassium hydroxide-catalyzed hydrosilylation exhibits excellent activity and chemoselectivity for the reduction of cyclic imides under mild reaction conditions. The chemoselectivity of the reduction system may be readily tuned by changing the identity an

Zinc-catalyzed selective reduction of cyclic imides with hydrosilanes: Synthesis of ω-hydroxylactams

Cyclic imides were selectively reduced to the corresponding ω-hydroxylactams in high yields with (EtO)3SiH (triethoxysilane) or PMHS (polymethylhydrosiloxane) under catalysis of zinc diacetate dehydrate [Zn(OAc)2 2H2O] (10%) and tetramethylethylenediamine (TMEDA) (10%). This catalytic protocol showed good functional group tolerance as well as excellent regioselectivity for unsymmetrical imides bearing coordinating groups adjacent to the carbonyl.

Regioselective Formation of Hydroxy Lactams from Pyridine-2,3-dicarboximides and their Cyclodehydration to Pyridopyrrolo-fused Heterocyclic Systems

Grignard reactions of pyridine-2,3-dicarboximides involve attack at the carbonyl group closer to the pyridine nitrogen atom to give 7-hydroxypyrrolopyridin-5(7H)-one derivatives.Reduction of the same imides with sodium borohydride gives mixtures of regiosomeric hydroxy lactams, in which the 7-hydroxypyrrolopyridin-5-ones are the major components.Hydroxy lactams derived by either of these two methods from pyridine-2,3-dicarboximides containing N-benzyl, N-2-phenylethyl, N-2-(indol-3-yl)ethyl, or N-biphenyl-2-yl substituents are cyclised by heating in trifluoroacetic or polyphosphoric acid to give derivatives of new pyridopyrrolo-fused heterocyclic systems.

Magnesium Ion Assisted Highly Regio- and Chemoselective Reduction of 5H-Pyrrolopyridine-5,7(6H)-diones with Sodium Borohydride. A Convenient Synthesis of 6,7-Dihydro-7-hydroxy-5H-pyrrolopyridin-5-ones

6-Substituted and unsubstituted 6,7-dihydro-7-hydroxy-5H-pyrrolopyridin-5-ones were predominantly obtained in excellent yield by the reduction of the corresponding 5,7-diones with sodium borohydride in the presence of Mg ion at 0 deg C.The highly r

New fused heterocyclic systems derived from pyridine-2,3-dicarboximides

α-Hydroxylactams (8), formed by regioselective reduction or Grignard addition to pyridine-2,3-dicarboximides (7), undergo acid-catalysed cyclodehydration to give the new pyrido[2′,3′: 3,4]-pyrrolo fused heterocyclic systems (10)-(13).