Selective C(sp³)–H Monoarylation Catalyzed by a Covalently Cross‐Linked Reverse Micelle‐Supported Palladium Catalyst

Abstract

In this work, we illustrate the performance of as olvated micelle-supported liganda saplatform for coordination with palladium for C-H arylation. Themicelle-supported ligandiso ne of the first applications of am icelle-supported ligand for C-H arylation, andprovides atunable support for future elaboration. Theu se of as patially constrained systemp ro-moted selectivity trends influenced by botht he sterics and electronics of the system, differing from the homogeneous catalyst, with high yields and selectivities.

Hydroaminoalkylation for the Catalytic Addition of Amines to Alkenes or Alkynes: Diverse Mechanisms Enable Diverse Substrate Scope

“…Jun and co-workers called the transformation a Csp 3 –H alkylation reaction rather than hydroaminoalkylation. This reaction is complementary to established Csp 3 –H alkylation cross-coupling strategies, with the added benefit of using simple alkenes as substrates rather than stochiometric-waste-generating transmetallating agents. ,,,,− Advances in late transition-metal hydroaminoalkylation are also complementary to early transition-metal catalysis. For example, late transition-metal catalysts typically display regioselectivity for the linear product, rather than the branched product.…”

“…The catalytic modification of amines and N -heterocycles is intensely investigated, as it is required to assemble selectively substituted amine products suitable for incorporation into biologically active agrochemicals or pharmaceuticals. These options include amine and N -heterocycle α-C–H oxidative and/or photocatalytic arylation/alkylation protocols, − and remote C–H alkylation for the synthesis of β- and γ-arylated/alkylated N -heterocycles. − Many of these C–H arylation/alkylation protocols require additives, cocatalysts, and activated substrates for coupling and often demand protection/deprotection protocols . These methods excel for Csp 3 –Csp 2 coupling while efficient approaches for Csp 3 –Csp 3 bond formation remain an area of ongoing investigation.…”

Micellar Catalysis as a Tool for C–H Bond Functionalization toward C–C Bond Formation

“…Jones later reported the first example of C­(sp 3 )–H monoarylation catalyzed by a cross-linked reverse micelle supported palladium­(II) catalyst . Reverse micelles were designed to promote selectivity trends influenced by the steric and electronic effects inside the micelle core (Figure ).…”

Shell Cross‐Linked Micelles as Nanoreactors for Enantioselective Three‐Step Tandem Catalysis

“…Other reported systems are based on blends of star polymers or core‐confined bottlebrush copolymers containing incompatible catalysts inside their cores that facilitate non‐orthogonal tandem transformations. Core functionalization is an attractive strategy because it allows for a high local concentration of catalysts that can result in rate acceleration effects and substrate selectivity . However, the main driving force for conversion in polymeric nanoreactors is the diffusion of substrates into the core.…”

“…Core functionalizationi sa na ttractive strategy becausei tallows for ah igh local concentration of catalysts that can result in rate acceleration effects [15] and substrate selectivity. [16][17][18] However, them ain driving force for conversion in polymericn anoreactors is the diffusion of substratesi nto the core. Therefore, as ingle system that compartmentalizes multiple catalysts would be advantageousi nt erms of substrate diffusion, as we have previously shownu sing shell cross-linked micelles (SCMs).…”