Shaoyu Mai

Substituent-Controlled Chemoselective Cleavage of C═C or Csp2–C(CO) Bond in α,β-Unsaturated Carbonyl Compounds with H-Phosphonates Leading to β-Ketophosphonates

An unprecedented substituent-controlled chemoselective cleavage of C═C double bond or C(sp(2))-C(CO) bond along with aerobic phosphorylation of α,β-unsaturated carbonyl compounds with H-phosphonates through a radical process has been disclosed. The current strategy provides an access to β-ketophosphonates under mild conditions with a wide substrate scope.

Cu-Catalyzed Synthesis of 3-Formyl Imidazo[1,2-a]pyridines and Imidazo[1,2-a]pyrimidines by Employing Ethyl Tertiary Amines as Carbon Sources

A highly efficient synthesis of 3-formyl imidazo[1,2-a]pyridine and imidazo[1,2-a]pyrimidine, under Cu-catalyzed aerobic oxidative conditions and by utilizing ethyl tertiary amines as carbon sources, is disclosed. A novel activation mode of ethyl tertiary amines in which simultaneous selective cleavage of C-C bond and C-N bond of ethyl group with molecular oxygen as terminal oxidant in this one-pot protocol is reported for the first time. This reaction features broad substrate scope, good functional group tolerance, as well as diversified and valuable products.

Divergent Synthesis of Disulfanes and Benzenesulfonothioates Bearing 2-Aminofurans From N-Tosylhydrazone-Bearing Thiocarbamates

An efficient and convenient synthesis of valuable disulfanes and benzenesulfonothioates, having a 2-aminofuran framework, has been developed by employing a copper-catalyzed transformation of readily available N-tosylhydrazone-bearing thiocarbamates. This method features an inexpensive metal catalyst, mild reaction conditions, good functional-group tolerance, short reaction times, and delivers valuable and complex products. A copper carbene generated from an N-tosylhydrazone-bearing thiocarbamate is proposed as the key intermediate for the transformation and it triggers the subsequent cascade. Remarkably, the Ts anion released from N-tosylhydrazone further serves as a nucleophile, thus rendering the formation of benzenesulfonothioates under controlled conditions.

Molecular-oxygen-promoted Cu-catalyzed oxidative direct amidation of nonactivated carboxylic acids with azoles

Summary A copper-catalyzed oxidative direct formation of amides from nonactivated carboxylic acids and azoles with dioxygen as an activating reagent is reported. The azole amides were produced in good to excellent yields with a broad substrate scope. The mechanistic studies reveal that oxygen plays an essential role in the success of the amidation reactions with copper peroxycarboxylate as the key intermediate. Transamidation occurs smoothly between azole amide and a variety of amines.

Thiocarbamate-Directed Tandem Olefination–Intramolecular Sulfuration of Two Ortho C–H Bonds: Application to Synthesis of a COX-2 Inhibitor

A palladium-catalyzed dual ortho C-H bond activation of aryl thiocarbamates is developed. This tandem reaction initiates by thiocarbamate-directed ortho C-H palladation, which leads to favorable olefin insertion rather than reductive elimination. The oxidative Heck reaction followed by another C-H activation and sulfuration affords the dual-functionalized products. This reaction provides a concise route to the S,O,C multisubstituted benzene skeleton which could be successfully applied for the synthesis of a COX-2 inhibitor.

Synthesis of fused benzimidazoles via successive nucleophilic additions of benzimidazole derivatives to arynes under transition metal-free conditions

An expedient and efficient strategy was developed for the synthesis of benzimidazole derivatives from aryne precursors with CsF and K2CO3 under transition metal-free conditions. The reaction exhibited good functional group tolerance, as substrates containing alkyls, ethers, nitryls, halogens etc., could all undergo the reaction smoothly, and afforded the desired products in good to excellent yields.

Cu-Catalyzed Denitrogenative Ring-Opening of 3-Aminoindazoles for the Synthesis of Aromatic Nitrile-Containing (Hetero)Arenes

An unprecedented Cu-catalyzed oxidative cleavage of two C-N bonds of 3-aminoindazoles is reported herein, which represents the first example for denitrogenative ring-opening of 3-aminoindazoles. This novel reactivity of 3-aminoindazoles enables the production of diverse aromatic nitrile-containing (hetero)arenes via C-H arylation of (hetero)arenes with wide subsrate scope under mild conditions.