95653-53-5

Upstream product

• 140-29-4 phenylacetonitrile 
• 127087-57-4 sodium sec-butoxide 
• 7402-45-1 α,α,α-tribromoacetophenone 
• 78-92-2 iso-butanol 
• 591-50-4 iodobenzene 
• 201230-82-2 carbon monoxide 
• 611-73-4 Benzoylformic acid 

Relevant academic research and scientific papers

Copper(II)-Catalyzed Benzylic C(sp3)-H Aerobic Oxidation of (Hetero)Aryl Acetimidates: Synthesis of Aryl-α-ketoesters

A straightforward method is developed in this paper for the synthesis of α-ketoesters through copper-catalyzed aerobic oxidation of (hetero)aryl acetimidates using molecular oxygen as a sustainable oxidant. The reaction represents the first example of the direct synthesis of aryl-α-ketoesters from arylacetimidates through the aerobic oxidation of a benzylic C(sp3)-H (CO) bond in moderate to good yield. This transformation occurs under mild reaction conditions with a wide range of substrates and utilizes a readily available oxidant and catalyst. The synthetic utility of this transformation is demonstrated through scaled-up synthesis. A plausible reaction mechanism is also proposed.

Reactions of benzoyl(carbonyl)transition metal complexes with LiNMe2: on the feasibility of a reaction route to α-keto amide through an acyl(carbamoyl)cobalt intermediate

CO-coordinated benzoyltransition metal complexes, PhCOCo(CO)3L (L = PPh3, PCy3, and PMe3), PhCOMn(CO)5, and PhCORe(CO)5, have been prepared and their reactions with LiNMe2 examined.The reactions give α-keto amide (PhCOCONMe2) after treating the system with Br2 or organic haldes.

PALLADIUM-CATALYZED DOUBLE CARBONYLATION REACTIONS OF ARYL HALIDES AFFORDING α-KETO ESTERS

Various aryl iodides can be converted into α-keto esters in reactions with carbon monoxide and alcohols in the presence of tertiary amines and catalytic amounts of tertiary phosphine-coordinated palladium complexes.

PHOTOINDUCED ALCOHOLYSIS OF alpha , alpha , alpha -TRIBROMACETOPHENONE TO BENZOYLFORMATE.

Irradiation of p-substituted alpha , alpha , alpha -tribromoacetophenones (1) in O//2-saturated alcohols (MeOH, prim. and sec. alcohols) afforded a new alcoholysis product, benzoylformate (2), in good yield (75-85%) along with benzoate and radical (reduction) products. Sensitization experiments showed that 2 was derived from the triplet excited 1. Formation of 2 as well as the decomposition rate of 1 were greatly accelerated by oxygen, presumably as a result of the involvement of the normally forbidden S//o yields T//1 transition of 1 due to the oxygen-1 charge transfer complex. Independent synthesis and reaction of possible intermediates in the photoalcoholysis of 1 leading to 2 suggested that 2 was formed from spontaneous (dark) reactions of initial photoalcoholysis product, alpha alpha -dibromo- alpha -alkoxyacetophenone.