87762-20-7

Upstream product

• 583-55-1 1-Bromo-2-iodobenzene 
• 141-43-5 ethanolamine 
• 627-11-2 2-Chloroethyl chloroformate 
• 615-36-1 2-bromoaniline 
• 325147-53-3 N-(2-(tert-butyldimethylsiloxy)-ethyl)-2-bromoaniline 
• 87762-16-1 2-(2-bromophenoxy)-N-(2-hydroxyethyl)acetamide 

Downstream Products

• 325147-44-2 N-(2-hydroxyethyl)-N-methyl-2-bromoaniline 
• 5735-53-5 1,4-benzoxazine 

Relevant academic research and scientific papers

Palladium-Catalyzed Aminomethylation and Cyclization of Enynol to O-Heterocycle Confined 1,3-Dienes

The rational tuning of the electrophilicity of the allylpalladium intermediates enables the regioselectively intramolecular 1,2-addition of enynol in the presence of aminal. This aminomethylation and cyclization reaction via C-N bond activation and intramolecular nucleophilic addition provides a rare example for the synthesis of O-containing heterocycle-confined 1,3-dienes, which is of synthetic potential for further derivatization. The method possesses broad substrate generality as well as functional group compatibility and efficiently affords a wide range of desired products with 5-, 6-, and 8-membered O-containing heterocycles with various functional groups.

Palladium-catalyzed intramolecular carbene insertion into C(sp3)-H bonds

A palladium-catalyzed carbene insertion into C(sp3)-H bonds leading to pyrrolidines was developed. The coupling reaction can be catalyzed by both Pd0 and PdII, is regioselective, and shows a broad functional group tolerance. This reaction is the first example of palladium-catalyzed C(sp3)-C(sp3) bond assembly starting from diazocarbonyl compounds. DFT calculations revealed that this direct C(sp3)-H bond functionalization reaction involves an unprecedented concerted metalation-deprotonation step. Pd in action: Palladium has been used to catalyze the C(sp3)-H insertion of metal carbenoids derived from α-diazoesters to form pyrrolidines through intramolecular assembly of C(sp3)-C(sp3) bonds. A reaction mechanism involving a metalation-deprotonation step instead of the usual concerted but asynchronous process is proposed.

Direct construction of fused indoles by gold-catalyzed cascade cyclization of conjugated diynes

A gold-catalyzed cascade cyclization of aniline derivatives bearing a conjugated diyne moiety was developed. Following the 5-endo-dig indole formation, subsequent 7-endo-dig cyclization predominated over 6-exo-dig cyclization to give the indole fused with a seven-membered ring in good yields.

Palladium-catalyzed intramolecular C-O bond formation

A number of oxygen heterocycles were synthesized using the palladium-catalyzed intramolecular etherification of aryl halides by employing di-tert-butylphosphinobiaryl ligands. The reaction proceeds under mild conditions using weak bases such as Cs2CO3 or K3PO4. A variety of functional groups are tolerated in the reaction, and enantioenriched alcohols can be coupled without erosion of optical purity. The mildness of the reaction conditions allows for the use of polyfunctionalized substrates. This method was used as the key step in the synthesis of MKC-242, an antidepressant currently in clinical trials. The synthesis of MKC-242 was achieved in 40% overall yield from commercially available sesamol and acrylonitrile.

Alkoxide-Accelerated Smiles Rearrangements. Synthesis of N-(2-Hydroxyethyl)anilines from N-(2-Hydroxyethyl)(aryloxy)acetamides

The first example of an alkoxide-accelerated Smiles rearrangement is reported.The rearrangement of N-(2-hydroxyethyl)(aryloxy)acetamides in dimethylformamide or tetrahydrofuran-18-crown-6 and potassium hydride produces useful yields of substituted N-(2-hydroxyethyl)anilines.