76403-17-3

Upstream product

• 492-37-5 hydratropic acid 
• 106-95-6 allyl bromide 
• 2613-89-0 phenylmalonic acid 
• 103-82-2 phenylacetic acid 
• 492-38-6 2-phenylacrylic acid 
• 31508-44-8 2-phenylpropionic acid methyl ester 
• 57625-76-0 methyl 2-methyl-2-phenyl-4-pentenoate 
• 591-87-7 Allyl acetate 
• 930100-99-5 diallyl 2-phenylmalonate 
• 930100-94-0 diallyl 2-methyl-2-phenylmalonate 
• 930101-02-3 dicrotyl 2-methyl-2-phenylmalonate 
• 930101-05-6 allyl 2-methyl-2-phenyl-4-pentenoate 
• 80765-43-1 phenyl 2-allyl-2-phenylpropionate 

Downstream Products

• 80765-43-1 phenyl 2-allyl-2-phenylpropionate 
• 76403-19-5 2-Methyl-2-phenyl-pent-4-enoyl azide 
• 57625-76-0 methyl 2-methyl-2-phenyl-4-pentenoate 
• 82461-15-2 2-methyl-2-phenylpent-4-en-1-ol 

Relevant academic research and scientific papers

Radical Aryl Migration from Boron to Carbon

Radical aryl migration reactions represent a unique type of organic transformations that involve the intramolecular migration of an aryl group from a carbon or heteroatom to a C- or heteroatom-centered radical through a spirocyclic intermediate. Various elements, including N, O, Si, P, S, Sn, Ge, and Se, have been reported to participate in radical aryl migrations. However, radical aryl migration from a boron center has not been reported to date. In this communication, radical 1,5-aryl migration from boron to carbon in aryl boronate complexes is presented. C-radicals readily generated through radical addition onto alkenyl aryl boronate complexes are shown to engage in 1,5-aryl migration reactions to provide 4-aryl-alkylboronic esters. As boronate complexes can be generatedin situby the reaction of alkenylboronic acid esters with aryl lithium reagents, the aryl moiety is readily varied, providing access to a series of arylated products starting from the same alkenylboronic acid ester via divergent chemistry. Reactions proceed with high diastereoselectivity under mild conditions, and also the analogous 1,4-aryl shifts are feasible. The suggested mechanism is supported by DFT calculations.

Siloxy Esters as Traceless Activators of Carboxylic Acids: Boron-Catalyzed Chemoselective Asymmetric Aldol Reaction**

The catalytic asymmetric aldol reaction is among the most useful reactions in organic synthesis. Despite the existence of many prominent reports, however, the late-stage, chemoselective, catalytic, asymmetric aldol reaction of multifunctional substrates is still difficult to achieve. Herein, we identified that in situ pre-conversion of carboxylic acids to siloxy esters facilitated the boron-catalyzed direct aldol reaction, leading to the development of carboxylic acid-selective, catalytic, asymmetric aldol reaction applicable to multifunctional substrates. Combining experimental and computational studies rationalized the reaction mechanism and led to the proposal of Si/B enediolates as the active species. The silyl ester formation facilitated both enolization and catalyst turnover by acidifying the α-proton of substrates and attenuating poisonous Lewis bases to the boron catalyst.

Iodoarene-Catalyzed Oxyamination of Unactivated Alkenes to Synthesize 5-Imino-2-Tetrahydrofuranyl Methanamine Derivatives

Reported here is the room-temperature metal-free iodoarene-catalyzed oxyamination of unactivated alkenes. In this process, the alkenes are difunctionalized by the oxygen atom of the amide group and the nitrogen in an exogenous HNTs2 molecule. This mild and open-air reaction provided an efficient synthesis to N-bistosyl-substituted 5-imino-2-tetrahydrofuranyl methanamine derivatives, which are important motifs in drug development and biological studies. Mechanistic study based on experiments and density functional theory calculations showed that this transformation proceeds via activation of the substrate alkene by an in situ generated cationic iodonium(III) intermediate, which is subsequently attacked by an oxygen atom (instead of nitrogen) of amides to form a five-membered ring intermediate. Finally, this intermediate undergoes an SN2 reaction by NTs2 as the nucleophile to give the oxygen and nitrogen difunctionalized 5-imino-2-tetrahydrofuranyl methanamine product. An asymmetric variant of the present alkene oxyamination using chiral iodoarenes as catalysts also gave promising results for some of the substrates.

Preparation of cyclic imides from alkene-tethered amides: Application of homogeneous Cu(ii) catalytic systems

A Cu-based homogeneous catalytic system was proposed for the preparation of imides from alkene-tethered amides. Here, O2 acted as a terminal oxidant and a cheap and easily available oxygen source. The cleavage of CC bonds and the formation of C

Copper(II)-Catalyzed Alkene Aminosulfonylation with Sodium Sulfinates for the Synthesis of Sulfonylated Pyrrolidones

A copper-catalyzed direct aminosulfonylation of unactivated alkenes with sodium sulfinates for the efficient synthesis of sulfonylated pyrrolidones is described. This reaction features good functional group tolerance and wide substrate scope, providing an efficient and straightforward protocol to access this kind of pyrrolidones. Moreover, preliminary mechanistic investigations disclosed that a free-radical pathway might be invovled in the process.

A 1,3,2-Diazaphospholene-Catalyzed Reductive Claisen Rearrangement

1,3,2-Diazaphospholenes (DAPs) are an emerging class of organic hydrides. In this work, we exploited them as efficient catalysts for very mild reductive Claisen rearrangements. The method is tolerant towards a wide variety of functional groups and operates at ambient temperature. Besides being enantiospecific for substrates with existing stereogenic centers, the diastereoselectivity can be switched by varying solvents and DAP catalysts. The reaction kinetics show direct rearrangements of O-bound phospholene enolates and provide a proof-of-principle for catalytic enantioselective reactions.

Chemo- and Enantioselective Pd/B Hybrid Catalysis for the Construction of Acyclic Quaternary Carbons: Migratory Allylation of O-Allyl Esters to α- C-Allyl Carboxylic Acids

We describe herein the asymmetric synthesis of α-allyl carboxylic acids containing an α-quaternary stereocenter by a chiral hybrid catalyst system comprising palladium and boron complexes. The reaction proceeded through palladium-catalyzed ionization of α,α-disubstituted O-allyl esters for the generation of chiral π-allyl palladium complex as an electrophile, boron-catalyzed enolization of the carboxylate part for the generation of chiral α,α-disubstituted carboxylic acid-derived enolates as a nucleophile, and enantioselective coupling between the thus-generated nucleophile and electrophile. Proper combinations of chiral ligands for the boron and palladium catalysts were crucial. The reaction proceeded chemoselectively at the α-position of the carboxylic acid group.

CuX2-mediated oxybromination/aminochlorination of unsaturated amides: Synthesis of iminolactones and lactams

We report herein a CuX2-mediated halocyclization of γ,δ-unsaturated amides for the synthesis of functionalized iminolactones and lactams respectively under mild reaction conditions. Mechanism studies indicated that N-attack cyclization was via a radical route while oxycyclization was via a nucleophilic attack on the activated CC bond.

Decarboxylative allylations of ester enolate equivalents

A variety of ester enolate equivalents are generated in situ and undergo α-allylation in high yields via palladium-catalyzed decarboxylative allylation. The transformations are complete within very short reaction times under ambient conditions. Synthesis of α-allylated acyl derivatives provides access to other carboxylic acid and alcohol derivatives via acyl group substitution or reduction. This journal is

Acyloxylactonisations mediated by lead tetracarboxylates

The reaction of lead(IV) tetracarboxylates with carboxylic acids containing unsaturated side chains has been found to give acyloxy lactone products in a diastereoselective process; the reaction can be extended to lead(IV) tetrazolates to give the analogous outcome. Mechanistic implications of these results are discussed.