23062-18-2

Upstream product

• 69460-11-3 (1R,2R,3R,5S)-(-)-Isopinocampheylamine 
• 3262-89-3 triphenylboroxine 
• 10281-53-5 trans-pinane 
• 582-61-6 benzoyl azide 

Downstream Products

• 23062-20-6 N-((1S,2R,3R,5R,6R)-6-Hydroxymethyl-2,6-dimethyl-bicyclo[3.1.1]hept-3-yl)-benzamide 
• 23062-20-6 N-((1S,2R,3S,5R,6R)-6-Hydroxymethyl-2,6-dimethyl-bicyclo[3.1.1]hept-3-yl)-benzamide 
• 23062-20-6 N-((1S,2S,3S,5R,6R)-6-Hydroxymethyl-2,6-dimethyl-bicyclo[3.1.1]hept-3-yl)-benzamide 
• 23062-20-6 N-((1S,2S,3R,5R,6R)-6-Hydroxymethyl-2,6-dimethyl-bicyclo[3.1.1]hept-3-yl)-benzamide 

Relevant academic research and scientific papers

Copper-Catalyzed C(sp3)?H Amidation: Sterically Driven Primary and Secondary C?H Site-Selectivity

Undirected C(sp3)?H functionalization reactions often follow site-selectivity patterns that mirror the corresponding C?H bond dissociation energies (BDEs). This often results in the functionalization of weaker tertiary C?H bonds in the presence of stronger secondary and primary bonds. An important, contemporary challenge is the development of catalyst systems capable of selectively functionalizing stronger primary and secondary C?H bonds over tertiary and benzylic C?H sites. Herein, we report a Cu catalyst that exhibits a high degree of primary and secondary over tertiary C?H bond selectivity in the amidation of linear and cyclic hydrocarbons with aroyl azides ArC(O)N3. Mechanistic and DFT studies indicate that C?H amidation involves H-atom abstraction from R-H substrates by nitrene intermediates [Cu](κ2-N,O-NC(O)Ar) to provide carbon-based radicals R. and copper(II)amide intermediates [CuII]-NHC(O)Ar that subsequently capture radicals R. to form products R-NHC(O)Ar. These studies reveal important catalyst features required to achieve primary and secondary C?H amidation selectivity in the absence of directing groups.

PROCESS FOR DIRECT AMIDATION OF AMINES VIA RH(I)-CATALYZED ADDITION OF BOROXINES

This invention relates to a process for making an amide by directly reacting a ferf-butyloxycarbonyl or carboxybenzyl N substituted amine with a boroxine derivative in the presence of a rhodium(l) catalyst, in the presence of a solvent an optionally in the presence of a base. The process provides means to react protected amines to amides using th boroganic reagent without the deprotection of an amine such that it can be directly converted from protected form in on step, and results in good yields in amide formation even for sterically hindered amines. Potassium fluoride is the preferre base in the reaction run in dioxane. Typical rhodium catalysts that can be used include rhodium(l) complex monomer and dimers such as chloro(1,5-cyclooctadiene) rhodium(l) dimer ("[CI(cod)Rh]2") or bis(1,5-cyclooctadiene)rhodium(l trifluoromethanesulfonate ("(cod)2Rh(OTf)").

Direct Amidation of N-Boc- and N-Cbz-Protected Amines via Rhodium-Catalyzed Coupling of Arylboroxines and Carbamates

N-Boc- and N-Cbz-protected amines are directly converted into amides by a novel rhodium-catalyzed coupling of arylboroxines and carbamates, replacing the traditional two-step deprotection-condensation sequence. Both protected anilines and aliphatic amines are efficiently transformed into a wide variety of secondary benzamides, including sterically hindered and electron-deficient amides, as well as in the presence of acid-labile and reducible functional groups.