Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions.

J Org Chem

State Key Laboratory of Chemistry and Utilization of Carbon-Based Energy Resources, Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education & Xinjiang Uygur Autonomous Region, Urumqi Key Laboratory of Green Catalysis and Synthesis Technology, College of Chemistry, Xinjiang University, Urumqi, Xinjiang 830017, P. R. China.

Published: August 2023

A palladium-catalyzed direct C-H arylation of indolines at C-7 position has been achieved at near-ambient temperature. The reaction was carried out with aryltriazene as a stable aryl source and electron shuttle to sustainably release aryl radical under the action of promoter, and pyrimidine as a detachable directing group for the synthesis of 7-arylindolines under oxidant- and ligand-free conditions. Notably, this catalytic system can also be applied to the direct and site-selective arylation of tetrahydroquinolines (C-8) and carbazoles (C-1).

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.joc.3c01022DOI Listing

Publication Analysis

Top Keywords

arylation indolines
8
pd-catalyzed c-7
4
c-7 arylation
4
indolines aryltriazenes
4
aryltriazenes mild
4
mild conditions
4
conditions palladium-catalyzed
4
palladium-catalyzed direct
4
direct c-h
4
c-h arylation
4

Similar Publications

2-(2-Nitrobenzyl)-2-(2-nitrophenyl)malonates, readily prepared by SAr-arylation of diethyl malonate with -fluoronitrobenzenes, followed by S2-alkylatioin of the resulting products with -nitrobenzyl bromides, undergo a tandem Fe/AcOH-promoted nitro-reduction and double lactamization sequence to afford spiro[indoline-3,3'-quinoline]-2,2'-diones in high overall yields. The method is operationally simple, economical, and has a broad substrate scope. The synthetic practicality of this methodology was illustrated by performing the reaction on a gram scale with the same efficiency.

View Article and Find Full Text PDF
Article Synopsis
  • This study outlines an efficient method to synthesize etrasimod, starting from a specific cyclopentenol compound, achieving a 5.6% yield with 98% enantiomeric excess.
  • A key intermediate was created through a unique rearrangement process that inverted the configuration of the starting compound.
  • The process included several stages to form a tetracyclic fused lactam and eventually produced cyclopenta[]indol-3-ylacetic acid by removing an oxo group and performing a series of reactions.
View Article and Find Full Text PDF

Controllable Synthesis of Cyclopenta[]indolines via Photocatalytic Fluoroalkylative Radical Cyclization Cascade of Ynamides.

Org Lett

June 2024

Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, Jinhua 321004, China.

A method for direct construction of cyclopenta[]indolines via a photocatalytic fluoroalkylative radical cyclization cascade of ynamides has been established, which proceeds via a sequence of radical addition, 1,5-HAT, 5-- cyclization, intramolecular arylation, and oxidative deprotonation. This protocol allows for the controllable assembly of a tricyclic architecture with three contiguous stereocenters, showcasing its high efficiency, compatibility, and regio- and diastereoselectivity for accessing pharmacologically significant fluoroalkylated cyclopenta[]indolines. It represents one of the very few examples of tetrafunctionalization of alkynes.

View Article and Find Full Text PDF

Palladium-Catalyzed Dearomative Heck/Suzuki Coupling of C2-Deuterated or C2-Nonsubstituted Indoles.

Org Lett

March 2024

College of Chemical Engineering, State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, Zhejiang University of Technology, Chaowang Road 18#, Hangzhou 310014, China.

A palladium-catalyzed dearomative diarylation of C2-deuterated or C2-nonsubstituted indoles through domino Heck/Suzuki coupling is established. Relying on electron-deficient phosphite ligand, side reactions including intermolecular Suzuki coupling and intramolecular C-D/H arylation are inhibited and a wide range of 2,3-diarylated indolines bearing vicinal tertiary stereocenters including deuterated ones are afforded in moderate to excellent yields (up to 94%) and excellent diastereoselectivities (>20:1). The catalyst loading can be lowered to 0.

View Article and Find Full Text PDF

Squaraine dyes possess sharp far-red active transition with high extinction coefficient and form aggregates on TiO surface. Aggregation of dyes on TiO has been considered as a detrimental factor for DSSC device performance, which can be controlled by appending alkyl groups to the dye structures. Hence by integrating alkylated (alkyl groups with both in-plane and out-of-plane) aryl group with indoline moiety to make it compatible with other electrolytes and for controlling the dye-aggregation, a series of squaraine acceptor-based dyes SQA4-6 have been designed and synthesized.

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!