81330-00-9

Upstream product

• 44855-57-4 rac-2-aminooctane 
• 98-59-9 p-toluenesulfonyl chloride 
• 4128-31-8 rac-octan-2-ol 
• 70-55-3 toluene-4-sulfonamide 
• 111-66-0 oct-1-ene 
• 696-62-8 para-iodoanisole 

Downstream Products

• 124920-18-9 2-methyl-5-propyl-1-tosylpyrrolidine 

Relevant academic research and scientific papers

Direct Synthesis of α-Amino Nitriles from Sulfonamides via Base-Mediated C-H Cyanation

Herein, we disclose a transition-metal-free reaction system that enables α-cyanation of sulfonamides through C-H bond cleavage for the preparation of α-amino nitriles, including difficult-to-access all-alkyl α-tertiary scaffolds. More than 50 substrate examples prove a wide functional group tolerance. Additionally, its synthetic practicality is highlighted by gram-scalability and the late-stage modification of natural compounds. Mechanistic experiments suggest that this process involves in situ formation of an imine intermediate via base-promoted elimination of HF.

Intermolecular Alkene Difunctionalization via Gold-Catalyzed Oxyarylation

The gold-catalyzed intermolecular oxyarylation of alkenes is reported. This work employed the oxidative addition of aryl iodides to Me?DalphosAu+ for the formation of a AuIII?Ar intermediate. The better binding ability of alkenes over O nucleophiles ensured the success of intermolecular oxyarylation, giving desired products with a broad substrate scope and high efficiency (>50 examples with up to 95 % yield). One-pot converting of methoxy groups into other nucleophiles allowed achieving alkene difunctionalization with the construction of C?N, C?S, and C?C bonds under mild conditions.

Copper-Catalyzed Amide Radical-Directed Cyanation of Unactivated Csp3-H Bonds

A method for site-selective intermolecular δ/?-Csp3-H cyanation of aliphatic sulfonamides is developed using TsCN as the cyanating reagent, catalyzed by a Cu(I)/phenanthroline complex. The mild, expeditious, and modular protocol allows efficient remote Csp3-H cyanation with good functional group tolerance and high regioselectivity. Mechanistic studies indicate that the reaction might proceed through a Cu(I)-mediated N-F bond cleavage to generate an amidyl radical, 1,5-HAT, and cyano group transfer of the resulting carbon radical with TsCN.

Mono- vs. dinuclear gold-catalyzed intermolecular hydroamidation

Mono- and dinuclear gold catalysts were investigated in the intermolecular hydroamidation of olefins. Upon activation of [Ph3PAuCl] and [xantphos(AuCl)2] with various silver salts (AgOTf, Ag[BF 4], and Ag[SbF6]), diverging reactivity of the resulting cationic gold complexes was observed. It was found that both the binding ability of the counterion and the solvent have a significant impact on the reactivity of the mono- and dinuclear complexes. Copyright

Gold versus silver-catalyzed intermolecular hydroaminations of alkenes and dienes

Comparative studies about the hydroamination of unactivated alkenes and dienes catalyzed by either cationic gold(I) triphenyl phosphite complexes or silver salts were performed using sulfonamides, anilines and carbamates as nucleophiles. Gold-catalyzed reactions generally, need lower loadings than those carried out with silver salts. Simple alkenes react only with sulfonamides and weak aromatic amines such as p-nitroaniline, whereas for conjugated dienes carbamates can also be used. Carbon-carbon double bond isomerization is observed only with gold similarly to when triflic acid was used, affording mixtures of regioisomeric products in the same cases. Silver-catalyzed hydroaminations failed with terminal alkenes, except with styrenes. Conjugate dienes can be hydroaminated either at 85 °C in toluene or at room temperature in dichloromethane. Non-conjugated 1,4- and 1,5-dienes suffer double hydroamination leading to saturated N-tosylated heterocyclic amines The catalytic cycle for the silver(I)-catalyzed hydroamination process has been computationally analyzed, resembling gold(I)-catalyzed processes, although with some significant differences. Copyright

Zirconium-catalyzed intermolecular hydroamination of unactivated olefins

Highly efficient hydroamination reactions of sulfonamides, carboxamides, and carbamates with unactivated olefins catalyzed by simple and inexpensive zirconium salts under mild reaction conditions were presented for the practical preparation of various amines. These processes gave good to excellent yields of the addition products in Markovnikov addition fashion. Georg Thieme Verlag Stuttgart.

InBr3 Catalyzed intermolecular hydroamination of unactivated alkenes

InBr3 has been demonstrated to be a simple catalyst for the intermolecular hydroamination of unactivated alkenes to produce tosyl- and mesyl-protected amines in moderate to good yields.

Gold(I)-catalyzed intra- and intermolecular hydroamination of unactivated olefins

Ph3PAuOTf catalyzes efficient intra- and intermolecular hydroamination of unactivated olefins with sulfonamides. Copyright

Hydroamination and hydroalkoxylation catalyzed by triflic acid. Parallels to reactions initiated with metal triflates

(Chemical Equation Presented) Intermolecular additions of the O-H bonds of phenols and alcohols and the N-H bonds of sulfonamides and benzamide to olefins catalyzed by 1 mol % of triflic acid and studies to define the relationship between these reactions and those catalyzed by metal triflates are reported. Cyclization of an alcohol containing pendant monosubstituted and trisubstituted olefins catalyzed by either triflic acid or metal triflates form products from addition to the more substituted olefin, and additions of tosylamide catalyzed by triflic acid or metal triflates form indistinguishable ratios of the two N-alkyl sulfonamides.

Mitsunobu-type alkylation of p-toluenesulfonamide. A convenient new route to primary and secondary amines

p-Toluenesulfonamide, which is known to form phosphine imides under Mitsunobu conditions, was shown to be alkylated in the presence of cyanomethylenetributylphosphorane to give N-substituted sulfonamides in excellent yields. The reaction can be applied to the synthesis of symmetrical and unsymmetrical N,N-disubstituted amides. When coupled with the desulfurization reactions, the reaction provides a new versatile synthetic route to primary and secondary amines from ammonia.