Sulfur-Directed α‑C(sp³)–H Amidation of Pyrrolidines with Dioxazolones under Rhodium Catalysis

Site-selective functionalization of saturated N-heterocycles such as pyrrolidines is a central topic in organic synthesis and drug discovery. We herein report the sulfur-assisted rhodium­(III)-catalyzed sp3 C–H amidation of pyrrolidines with dioxazolones as amidating agents. The amenability of the thioamide directing group is elucidated by a series of control experiments

Sulfur-Directed α‑C(sp³)–H Amidation of Pyrrolidines with Dioxazolones under Rhodium Catalysis

Site-selective functionalization of saturated N-heterocycles such as pyrrolidines is a central topic in organic synthesis and drug discovery. We herein report the sulfur-assisted rhodium­(III)-catalyzed sp3 C–H amidation of pyrrolidines with dioxazolones as amidating agents. The amenability of the thioamide directing group is elucidated by a series of control experiments

Synthesis of 2‑Formyl Carbazoles via Tandem Reaction of Indolyl Nitrones with 2‑Methylidene Cyclic Carbonate

The synthesis of functionalized carbazoles as privileged nitrogen heterocycles has emerged as a central topic in drug discovery and material science. We herein disclose the rhodium­(III)-catalyzed cross-coupling reaction between indolyl nitrones and 2-methylidene cyclic carbonate as an allylating surrogate, resulting in the formation of C2-formylated carbazoles via tandem C–H allylation, [3 + 2] cycloaddition, aromatization, and benzylic oxidation. The synthetic utility of this protocol is highlighted by a variety of post-transformations of C2-formylated carbazoles

Synthesis of 2‑Formyl Carbazoles via Tandem Reaction of Indolyl Nitrones with 2‑Methylidene Cyclic Carbonate

The synthesis of functionalized carbazoles as privileged nitrogen heterocycles has emerged as a central topic in drug discovery and material science. We herein disclose the rhodium­(III)-catalyzed cross-coupling reaction between indolyl nitrones and 2-methylidene cyclic carbonate as an allylating surrogate, resulting in the formation of C2-formylated carbazoles via tandem C–H allylation, [3 + 2] cycloaddition, aromatization, and benzylic oxidation. The synthetic utility of this protocol is highlighted by a variety of post-transformations of C2-formylated carbazoles

Catalyst-Controlled C–H Allylation and Annulation of 2‑Aryl Quinazolinones with 2‑Methylidene Cyclic Carbonate

The site-selective modification of quinazolinone as a privileged bicyclic N-heterocycle is an attractive topic in medicinal chemistry and material science. We herein report the ruthenium­(II)-catalyzed C–H allylation of 2-aryl quinazolinones with 2-methylidene cyclic carbonate. In addition, tandem C–H allylation and annulation are achieved under rhodium­(III) catalysis, resulting in the formation of tetracyclic quinazolinones including a tertiary carbon center. Post-transformations of the synthesized products demonstrate the potential of the developed methodology. A series of mechanistic investigations were also performed

Catalyst-Controlled C–H Allylation and Annulation of 2‑Aryl Quinazolinones with 2‑Methylidene Cyclic Carbonate

The site-selective modification of quinazolinone as a privileged bicyclic N-heterocycle is an attractive topic in medicinal chemistry and material science. We herein report the ruthenium­(II)-catalyzed C–H allylation of 2-aryl quinazolinones with 2-methylidene cyclic carbonate. In addition, tandem C–H allylation and annulation are achieved under rhodium­(III) catalysis, resulting in the formation of tetracyclic quinazolinones including a tertiary carbon center. Post-transformations of the synthesized products demonstrate the potential of the developed methodology. A series of mechanistic investigations were also performed