Transition metal and reductant free α-C(sp3)–H hydroxylation of carbonyl compounds are reported. This method is promoted by commercially available inexpensive KO-t-Bu atmospheric air as an oxidant at room temperature. unified strategy also very facile for various compound derivatives to obtain quaternary hydroxyl in excellent yield. A preliminary mechanistic investigation, supported isotope labeling computational studies, suggests the formation a peroxide bond its cleavage situ generated enolate.

Abstract An asymmetric enantioselective flow process is reported for the formal synthesis of a 1,2,3,4‐tetrahydroquinoline selective estrogen receptor modulator. Starting from an easily available 2‐nitrochalcone, first part comprised telescoped nitro reduction/intramolecular cyclocondensation sequence using diboronic acid as simple reductant. Subsequent transfer hydrogenation in presence immobilized phosphoric organocatalyst followed by N ‐alkylation furnished targeted chiral intermediate....

Iron-catalyzed dehydrogenative cross-coupling of carbonyl compounds with aliphatic peroxide was developed under mild conditions. A library linear alkylated and arylated peroxides are synthesized in good to excellent yield. This method is highly selective general for a range biologically important derivatives 2-oxindole, barbituric acid, 4-hydroxy coumarin functional group tolerance without the cleavage bond. peroxidation reaction upscalable grams also synthesizable continuous flow increased...

Abstract The enantioselective Pictet‐Spenlger reaction of tryptamines and diketo compounds catalyzed by a polymer‐supported phosphoric acid (TRIP) has been accomplished for the first time in continuous flow. Using this approach, diverse library quaternary tryptolines synthesized 36–95% yield with 39–99% enantiomeric excess. scalability demonstrated flow, residence only 24 minutes. robust immobilized catalyst recycled reused multiple times batch synthesis chiral precursors Tadalafil,...

The highly efficient direct α-alkylation of unactivated amides has been accomplished using alcohols in the presence Ru-PNN catalyst (0.1 mol%) with a high turnover number. Using this approach, 2-oxindole was directly transformed into C3-alkylated 3-hydroxyindolin-2-one one step without use any oxidant.

An unprecedented skeletal rearrangement of 3-(tert-butylperoxy)indolin-2-one using a tin catalyst has been developed. This is highly selective to afford series fluorophoric (Z)-2-arylidene and alkylidene-2H-benzo[b][1,4]oxazin-3(4H)-one derivatives in good excellent yield. In contrast with Sn(OTf)2, the reaction FeCl3 afforded Hock fragmentation product via C–C bond cleavage.

Direct α-alkylation of amides and the synthesis C3-alkylated 3-hydroxyindolin-2-one/2-substituted-2-hydroxy-3,4-dihydronaphthalen-1(2H)-one derivatives from 2-oxindole/1-teralone were reported using primary alcohols in presence Ru-NHC catalyst a one pot condition under borrowing hydrogen method. In case inert conditions, exclusively forms product. Whereas, allowing this reaction mixture to occur an air atmosphere predominantly 3-hydroxyindolin-2-one via domino C-H alkylation aerobic...

Highly efficient, selective, and direct C–H peroxidation of 9-substituted fluorenes has been achieved using a Mn–2,2′-bipyridine catalyst via radical–radical cross-coupling. Moreover, this method effectively promotes the vicinal bisperoxidation sterically hindered various substituted arylidene-9H-fluorene/arylideneindolin-2-one derivatives to afford highly bisperoxides with high selectivity over oxidative cleavage C═C bond that usually forms ketone an aldehyde. Furthermore, new approach for...

A base-free and acceptorless Ru-catalyzed dehydrogenative approach has been developed for the synthesis of N-heterocycles by using 1,3-dicarbonyls amino alcohols through a domino sequential enamine formation intramolecular oxidative cyclization strategy. This unified is also applicable O-heterocycles involving 2-hydroxybenzyl alcohol as coupling reactant via consecutive C-alkylation steps. The present protocol general varieties biologically important scaffolds, such...

We have demonstrated the magnetically retrievable Fe(OH)₃Fe₃O₄catalyzed C–H peroxidation of 2-oxindole and barbituric acid derivatives under batch continuous flow process for first time.

We report here the Sn-catalyzed mild protocol for ring expansion of peroxyoxindoles to afford series substituted-2H-benzo[b][1,4]oxazin-3(4H)-one derivatives. In this protocol, we showed in situ conversion tert-butyl peroxy compounds into peresters with aid external esters, which then underwent ring-expansion process, and incipient carbocation was trapped alcohol residue generated from esters. The reaction is also demonstrated a continuous flow process rearranged product 22 min residence time.

Ru(<sc>ii</sc>)-NHC catalyzes α-olefination of 2-oxindole <italic>via</italic> dehydrogenative coupling and diaryl methanol to generate selectively antimalarial 3-(diphenylmethylene)indolin-2-one derivatives.

A polystyrene-supported N-heterocyclic organocatalyst is shown to be a versatile system for the N -formylation of amines using carbon dioxide and silanes, heterogeneous catalyst can potentially applied under continuous flow.

A family of polystyrene-supported (phosphoramidite, olefin) ligands L1-L4, based on the original design by Defieber and Carreira, has been developed applied in iridium-catalyzed asymmetric allylic amination unmasked alcohols (27 examples, up to 99% ee). Among them, functional resins L1 L4 exhibit important advantages such as easy preparation, ligand recyclability, handling for sequential use. As a distinctive advantage, catalytic use iridium complexes allows straightforward reuse high...

Fe-catalyzed direct transformation of nitro compounds to aldehyde under batch/continuous flow module is reported. This catalytic highly selective for syntheses various aldehydes and does not require any additional additives such as bases oxidants. Furthermore, the heterogeneous Fe–zeolite catalyst recoverable reusable more than five cycles offers gram-scale synthesis without loss efficiency. has a maximum TOF 5.93 h–1.

An environmentally benign approach for the synthesis of vinylogous esters from 1,3-diketone and its reverse reaction under continuous-flow has been developed with alcohols in presence inexpensive Amberlyst-15 as a catalyst. This methodology is highly selective general range cyclic 1,3-dicarbonyl compounds which gives library linear alkylated arylated good to excellent yield solvent metal free condition. Furthermore, long-time experiment up 40 h afforded 8.0 g ester turnover number (TON) =...

When mixed with 2% by weight of either KMnO4, Ba(MnO4)2 or NH4MnO4, an enhanced thermal decomposition cubic ammonium perchlorate, AP, was observed over the temperature range 255–300‡. A still more pronounced effect when AP subjected to a radiation dose 10 Mrad. The activation energy involved acceleratory stage found be 46 kJ mol−1 for irradiated as against normal value 85 mol−1. remained unaltered in case first two additives, while presence NH4MnO4 it decreased 55 Neutron bombardment did not...

A solvent-free enantioselective Michael addition mediated by a polymer-supported Jørgensen–Hayashi catalyst and domino Pictet–Spengler plus lactamisation sequence has been reported in continuous flow.