Rhodium(III)-Catalyzed Cascade Cyclization/Electrophilic Amidation for the Synthesis of 3‑Amidoindoles and 3‑Amidofurans

A rhodium­(III)-catalyzed cascade cyclization/electrophilic amidation using <i>N</i>-pivaloyloxylamides as the electrophilic nitrogen source has been developed. This protocol provides an efficient route for the synthesis of 3-amidoindoles and 3-amidofurans under mild conditions with good functional group tolerance. The synthetic utility of this reaction has been demonstrated through the derivatization of the 3-amidoindoles to several heterocycle-fused indoles

Rhodium(III) Catalyzed Carboamination of Alkenes Triggered by C–H Activation of <i>N</i>‑Phenoxyacetamides under Redox-Neutral Conditions

<i>N</i>-Alkoxyacrylamides are coupled with <i>N</i>-phenoxyacetamides by Rh^III catalysis through C–H functionalization and amido group transfer under external oxidant-free conditions, which affords acyclic alkene carboamination products in an atom-economical way. Mechanistic insight into this transformation indicates the amide group in <i>N</i>-alkoxyacrylamide plays a critical role in this C–C/C–N bond formation reaction. This methodology provides a highly efficient way to construct <i>o</i>-tyrosine derivatives under mild conditions

Rhodium(III)-Catalyzed Cascade Cyclization/Electrophilic Amidation for the Synthesis of 3‑Amidoindoles and 3‑Amidofurans

A rhodium­(III)-catalyzed cascade cyclization/electrophilic amidation using <i>N</i>-pivaloyloxylamides as the electrophilic nitrogen source has been developed. This protocol provides an efficient route for the synthesis of 3-amidoindoles and 3-amidofurans under mild conditions with good functional group tolerance. The synthetic utility of this reaction has been demonstrated through the derivatization of the 3-amidoindoles to several heterocycle-fused indoles

Regiocontrolled Coupling of Aromatic and Vinylic Amides with α‑Allenols To Form γ‑Lactams via Rhodium(III)-Catalyzed C–H Activation

A mild, regiocontrolled coupling of aromatic and vinylic amides with α-allenols to form γ-lactams via rhodium­(III)-catalyzed C–H activation has been demonstrated. This [4 + 1] annulation reaction provides an efficient method for the synthesis of isoindolinones and 1,5-dihydro-pyrrol-2-ones bearing a tetrasubstituted carbon atom α to the nitrogen atom with good functional group tolerance. The hydroxyl group in the allene substrate is essential in controlling the chemo- and regioselectivity of the reaction probably by coordination interaction with the rhodium catalyst

Rhodium(III) Catalyzed Carboamination of Alkenes Triggered by C–H Activation of <i>N</i>‑Phenoxyacetamides under Redox-Neutral Conditions

<i>N</i>-Alkoxyacrylamides are coupled with <i>N</i>-phenoxyacetamides by Rh^III catalysis through C–H functionalization and amido group transfer under external oxidant-free conditions, which affords acyclic alkene carboamination products in an atom-economical way. Mechanistic insight into this transformation indicates the amide group in <i>N</i>-alkoxyacrylamide plays a critical role in this C–C/C–N bond formation reaction. This methodology provides a highly efficient way to construct <i>o</i>-tyrosine derivatives under mild conditions

Manganese-Catalyzed Asymmetric Hydrosilylation of Aryl Ketones

We disclose the synthesis of a series of manganese complexes of chiral iminopyridine oxazoline ligands and their application in the first manganese-catalyzed asymmetric ketone hydrosilylations. The most sterically hindered manganese catalyst bearing two CH­(Ph)₂ groups at the 2,6-ortho positions of the imino aryl ring and a <i>t</i>Bu group on the oxazoline ring furnishes the secondary alcohols in high enantioselectivities and yields

Rhodium(III)-Catalyzed C–H Olefination for the Synthesis of <i>ortho</i>-Alkenyl Phenols Using an Oxidizing Directing Group

By using an oxidizing directing group, a mild, efficient Rh(III) catalyzed C–H olefination reaction between <i>N</i>-phenoxyacetamides and alkenes was developed. This reaction provided a straightforward way for the synthesis of <i>ortho</i>-alkenyl phenols, and the directing group is traceless in the product

Cascade Synthesis of 3‑Alkylidene Dihydrobenzofuran Derivatives via Rhodium(III)-Catalyzed Redox-Neutral C–H Functionalization/Cyclization

An efficient rhodium­(III)-catalyzed coupling reaction of <i>N</i>-phenoxyacetamides with propargyl carbonates to yield 3-alkylidene dihydrobenzofuran derivatives via C–H functionalization/cascade cyclization has been developed. This transformation represents a redox-neutral process and features the formation of three new bonds under mild conditions

Ruthenium-Catalyzed Site-Selective Intramolecular Silylation of Primary C–H Bonds for Synthesis of Sila-Heterocycles

Incorporating the silicon element into bioactive organic molecules has received increasing attention in medicinal chemistry. Moreover, organosilanes are valuable synthetic intermediates for fine chemicals and materials. Transition metal-catalyzed C–H silylation has become an important strategy for C–Si bond formations. However, despite the great advances in aromatic C­(sp²)–H bond silylations, catalytic methods for aliphatic C­(sp³)–H bond silylations are relatively rare. Here we report a pincer ruthenium catalyst for intramolecular silylations of various primary C­(sp³)–H bonds adjacent to heteroatoms (O, N, Si, Ge), including the first intramolecular silylations of C–H bonds α to O, N, and Ge. This method provides a general, synthetically efficient approach to novel classes of Si-containing five-membered [1,3]-sila-heterocycles, including oxasilolanes, azasilolanes, disila-heterocycles, and germasilolane. The trend in the reactivity of five classes of C­(sp³)–H bonds toward the Ru-catalyzed silylation is elucidated. Mechanistic studies indicate that the rate-determining step is the C–H bond cleavage involving a ruthenium silyl complex as the key intermediate, while a η²-silene ruthenium hydride species is determined to be an off-cycle intermediate

The performance of difference inference methods in the external validation set of GPCRs and kinases.

<p>All performances were evaluated based on top 20 predicted lists. NBI, network-based inference; NWNBI, node weighted network-based inference; EWNBI, edge weighted network-based inference; DBSI-T, drug-based similarity inference with Tanimoto similarity score; DBSI-C, DBSI with Cosine similarity score; DBSI-F, DBSI with Forbes similarity score; DBSI-R, DBSI with Russell-rao similarity score; TBSI, target-based similarity inference; R, recall; ER, recall enhancement; AUC, the area under the receiver operating characteristic curve; C_i (P_a, P_b, …, P_m) represents the prioritization of new targets for a given chemical; P_j (C_a, C_b, …, C_n) represents the prioritization of new chemicals for a given protein.</p