Rhodium(III)-Catalyzed Intermolecular Direct Amidation of Aldehyde C–H Bonds with <i>N</i>‑Chloroamines at Room Temperature

A Rh(III)-catalyzed direct aldehyde C–H amidation from aldehydes and N-chloroamines, prepared in situ from amines, has been developed via C–H bond activation under very mild reaction conditions. A variety of primary and secondary amines were used to afford the corresponding amides in moderate to excellent yields

Iridium(III)-Catalyzed C‑7 Selective C–H Alkynylation of Indolines at Room Temperature

An iridium-catalyzed direct C-7 selective C–H alkynylation of indolines at room temperature, for the first time, has been developed via C–H bond activation. Furthermore, the first example of direct C–H alkynylation of carbazoles at the C1 position is also achieved. More importantly, the resulting product can be readily transformed into C7-alkynylated indoles, further widening the C-7 derivatization of indoles and highlighting the synthetic utility of this methodology

Rhodium(III)-Catalyzed Intermolecular Direct Amidation of Aldehyde C–H Bonds with <i>N</i>‑Chloroamines at Room Temperature

A Rh(III)-catalyzed direct aldehyde C–H amidation from aldehydes and <i>N</i>-chloroamines, prepared in situ from amines, has been developed via C–H bond activation under very mild reaction conditions. A variety of primary and secondary amines were used to afford the corresponding amides in moderate to excellent yields

Iridium(III)-Catalyzed C‑7 Selective C–H Alkynylation of Indolines at Room Temperature

An iridium-catalyzed direct C-7 selective C–H alkynylation of indolines at room temperature, for the first time, has been developed via C–H bond activation. Furthermore, the first example of direct C–H alkynylation of carbazoles at the C1 position is also achieved. More importantly, the resulting product can be readily transformed into C7-alkynylated indoles, further widening the C-7 derivatization of indoles and highlighting the synthetic utility of this methodology

Rhodium-Catalyzed Direct Addition of Aryl C–H Bonds to Nitrosobenzenes at Room Temperature

An unprecedented Rh-catalyzed direct addition of aryl C–H bonds to nitrosobenzenes has been developed under very mild reaction conditions (room temperature). The reaction is highly step-, atom-, and redox-economic and compatible with air and water to <i>N</i>-selectively provide a variety of <i>N</i>-diarylhydroxylamines in good to excellent yields. More importantly, this process may provide a new direction for C–N bond formation through direct C(sp²)–H functionalization

Synthesis of Six-Membered Spirocyclic Oxindoles with Five Consecutive Stereocenters in an Asymmetric Organocatalytic One-Pot Michael/Michael/Aldol Addition Sequence

An asymmetric organocatalytic one-pot synthesis of six-membered spirocyclic oxindoles has been successfully developed through a relay Michael/Michael/aldol addition reaction catalyzed by the combination of readily available diphenylprolinol silyl ether and bifunctional quinine thiourea. The one-pot protocol affords the highly substituted spirocyclic oxindoles in high yields and perfect enantioselectivities. More importantly, through judicious choice of the organocatalysts employed, this reaction could be readily adapted to predominantly afford an alternative major diastereomer of the product

Copper(I)-Catalyzed Aryl or Vinyl Addition to Electron-Deficient Alkenes Cascaded by Cationic Cyclization

An exoselective copper-catalyzed arylation– and vinylation–carbocyclization of electron-deficient alkenes was developed to provide rapid and efficient access to a variety of functionalized 3,3-disubstituted oxindoles. With this method, a highly efficient and concise formal synthesis of (±)-physostigmine and (±)-physovenine has been completed

Rh(III)-Catalyzed C–H Amidation with <i>N</i>‑Hydroxycarbamates: A New Entry to <i>N</i>‑Carbamate-Protected Arylamines

An unprecedented Rh­(III)-catalyzed direct intermolecular C–H amidation with <i>N</i>-hydroxycarbamates has been developed. Different directing groups, such as pyridine, pyrimidine, pyrazole, and <i>N</i>-OMe oxime, can be employed in this C–H amidation process, providing valuable <i>N</i>-carbamate-protected arylamines (e.g., Cbz, Moz, Ac, Boc, and Fmoc). More importantly, this process may afford a new avenue for intermolecular C–H amidation where readily available <i>N</i>-hydroxycarbamates can be used as the nitrogen sourc

Ruthenium(II)-Catalyzed Regioselective Ortho C–H Allenylation of Electron-Rich Aniline and Phenol Derivatives

Ortho C–H allenylation of electron-rich benzene derivatives with propargylic alcohol derivatives has been a challenge, due to their great innate tendency toward a para C–H allenylation via an SN2′-type substitution process. Here, we described a Ru­(II)-catalyzed regioselective ortho C–H allenylation of electron-rich aniline and phenol derivatives, which allows the previously challenging synthesis of a broad range of ortho allenylated aniline and phenol derivatives. More significantly, highly optically active fully substituted allenes can also be prepared with high enantiomeric excess via a highly efficient chirality transfer. No para C–H allenylation product was observed in the current catalytic system, thus showing a complete reversibility of the regioselectivity

Rh(III)-Catalyzed Addition of Alkenyl C–H Bond to Isocyanates and Intramolecular Cyclization: Direct Synthesis 5‑Ylidenepyrrol-2(5<i>H</i>)‑ones

The rhodium-catalyzed addition of an alkenyl C–H bond to isocyanates via sp² C–H bond activation followed by an intramolecular cyclization is described. This atom-economic and catalytic reaction affords a simple and straightforward access to biologically relevant 5-ylidene pyrrol-2(5<i>H</i>)-ones and can be carried out under mild and neutral conditions in the absence of any additives and environmentally hazardous waste production