This study analyzes the feasibility of utilizing the catalytic and enantioselective [4 + 2] cycloaddition of sterically demanding heterocycle-incorporated siloxydienes to yield polycyclic skeletons with a tetrasubstituted carbon. A catalyst derived from lanthanide triflimide enabled the reaction. The mechanistic investigations and transformations of the adducts are also discussed. The proposed approach facilitates the synthesis of intricate polysubstituted skeletons, each with multiple contiguous chiral centers, thereby aiding in the production of diverse hydrocarbazoles for drug discovery purposes.

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.joc.4c00837DOI Listing

Publication Analysis

Top Keywords

tetrasubstituted carbon
8
enantioselective cycloaddition
8
synthesizing chiral
4
chiral hydrocarbazoles
4
hydrocarbazoles tetrasubstituted
4
carbon holmium-catalyzed
4
holmium-catalyzed enantioselective
4
cycloaddition mechanistic
4
mechanistic insights
4
insights luminescence
4

Similar Publications

Zero-Valent Copper Catalysis Enables Regio- and Stereoselective Difunctionalization of Alkynes.

Angew Chem Int Ed Engl

January 2025

Jain University - Ramanagara Campus, Centre for Nano and Material Sciences, Jakkasandra Post Kanakapura Taluk, Ramanagara-562112, Bangalore, 562112, Bangalore, INDIA.

The development of a metallic copper-based catalyst system remains a significant challenge. Herein, we report the synthesis of highly stable, active, and reusable Cu0 catalyst for the carboboration of alkynes using carbon electrophiles and bis(pinacolato)diboron (B2pin2) as chemical feedstocks to afford di- and trisubstituted vinylboronate esters in a regio- and stereoselective manner with appreciable turnover number (TON) of up to 2535 under mild reaction conditions. This three-component coupling reaction works well with a variety of substituted electrophiles and alkynes with broad functional group tolerance.

View Article and Find Full Text PDF

Amide-Directed Highly Enantioselective Hydrogenation of Diverse Acyclic Multisubstituted Alkenes Under Mild Conditions.

Angew Chem Int Ed Engl

January 2025

Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, 100084, China.

Enantioselective hydrogenation of tetrasubstituted alkenes to form 1,2-contiguous stereocenters is a particularly appealing but highly challenging transformation in asymmetric catalysis. Despite the notable progress achieved in enantioselective hydrogenation over the past decades, enantioselective hydrogenation of all-carbon tetrasubstituted alkenes containing multiple alkyl groups remains an unsolved challenge. Here, we report a rhodium-catalyzed highly diastereo- and enantioselective hydrogenation of diverse acyclic multisubstituted alkenes under mild conditions.

View Article and Find Full Text PDF

A straightforward and highly diastereoselective synthesis of -4-hydroxypiperidines is presented. This method allows access to C2 and C4 substituted piperidines, bearing a tetrasubstituted carbon stereocenter at C4. -Disubstituted homoallylic amines and ketoaldehydes as carbonyl partners have been rarely used in aza-Prins cyclizations, expanding the scope of this reaction.

View Article and Find Full Text PDF

This study introduces a novel methodology for the direct construction of tetrasubstituted centers, utilizing secondary C(sp)-H and C(sp)-H substrates, specifically indolin-2-ones and indoles, through an innovative oxidative cross-coupling reaction. Facilitated by a straightforward copper salt catalyst, this reaction proceeds efficiently at a mild temperature of 40 °C under operationally streamlined conditions. Emphasizing sustainability, this method is notably enhanced by employing air (molecular oxygen) as an eco-friendly oxidant.

View Article and Find Full Text PDF

A sequential [3 + 2]/[2 + 1] annulation reactions of benzimidazole- and indole-derived acrylonitriles with vinylsulfonium salts have been developed for the first time, and shown to provide in yields of 32 to 98% a series of azabicyclo[3.1.0]hexanes containing each a cyano-substituted tetrasubstituted carbon stereocenter with >20 : 1 dr.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!