97462-62-9

Upstream product

• 97462-61-8 N-(3-butenyl)-N-<(phenylthio)methyl>benzenemethanamine 
• 121897-89-0 Allyl-benzyl-methyl-trimethylsilanylmethyl-ammonium; bromide 
• 5162-44-7 1-bromo-4-butene 
• 103-67-3 benzyl-methyl-amine 
• 4784-77-4 (E)-1-Bromo-2-butene 
• 50-00-0 formaldehyd 
• 102234-85-5 N-benzyl-N-methylammonium trifluoroacetate 
• 762-72-1 allyl-trimethyl-silane 
• 106-99-0 buta-1,3-diene 
• 75-11-6 diiodomethane 
• 2520-97-0 N-allyl-N-α-methylbenzylamine 
• 17150-62-8 N-benzyl-3-butenylamine 
• 100-46-9 benzylamine 
• 51951-99-6 N-benzyl-N-methyl-1-(trimethylsilyl)methanamine 

Relevant academic research and scientific papers

Tandem formation and [2,3] rearrangement of methylene ammonium ylides derived from amines and the Simmons-Smith reagent

(Matrix presented) Zinc-complexed methylene ammonium ylides are formed from tertiary amines and the Simmons-Smith reagent. These stable entities can be activated with n-BuLi to allow reactions typical of ammonium ylides such as [2,3] rearrangements. In th

A general nickel-catalyzed hydroamination of 1,3-dienes by alkylamines: Catalyst selection, scope, and mechanism

A simple colorimetric assay of various transition-metal catalysts showed that the combination of DPPF, Ni(COD)2, and acid is a highly active catalyst system for the hydroamination of dienes by alkylamines to form allylic amines. The scope of the reaction is broad; various primary and secondary alkylamines react with 1,3-dienes in the presence of these catalysts. Detailed mechanistic studies revealed the individual steps involved in the catalytic process. These studies uncovered unexpected thermodynamics for the addition of amines to π-allyl nickel complexes: instead of the thermodynamics favoring the reaction of a nickel allyl with an amine to form an allylic amine, the thermodynamics favored reaction of a nickel(0) complex with allylic amine in the presence of acid to form a Ni(II) allyl. The realization of these thermodynamics led us to the discovery that nickel and some palladium complexes in the presence or absence of acid catalyze the exchange of the amino groups of allylic amines with free amines. This exchange process was used to reveal the relative thermodynamic stabilities of various allylic amines. In addition, this exchange reaction leads to racemization of allylic amines. Therefore, the relative rate for C-N bond formation and cleavage influences the enantioselectivity of diene hydroaminations.

Sigmatropic Rearrangements of N-Benzyl-N-methyl-N-(2-alkenyl)ammonium N-Methylides

Fluoride-ion induced desilylation of N-benzyl-N-methyl-N-(2-alkenyl)-N-ammonium halides gave N-methylide intermediates which were isomerized to N-methyl-N-(2-alkenyl)-2-methylbenzylamines (Sommelet-Hauser rearrangement products) an

Reactions of Allystannanes with in Situ Generated Immonium Salts in Protic Solvent: A Facile Aminomethano Destannylation Process

In situ generated immoniunm salts derived from primary amines and formaldehyde upon exposure to allylstannanes in protic media undergo rapid, facile aminomethano destannylation, giving rise to bishomoallylamines with no evidence of piperidine formation.

Utilization of Phenylthio Substituted Amines for the Synthesis of Pyrrolidines

α-Phenylthio substituted amines have been found to be convenient reagents for the preparation of the pyrrolidine ring.Benzylamine (2) undergoes 1,3-dipolar cycloaddition with several dipolarophiles in the presence of silver fluoride.The reaction is believed to proceed via the intermediacy of an azomethine ylide.Treatment of α-(phenylthio)cyanoamines 10 and 17 with strong base results in the loss of the phenylthio group, and formation of substituted trans-piperazines 21, 22 in the case of 17.The mechanism of the reaction involves dimerization of the initially formed cyano substituted azomethine ylide intermediate, which behaves as a captodative diradical.Finally, the reaction of several alkenylamines with tributyltin hydride was studied as a method for generating the pyrrolidine ring via a radical cyclization reaction.

Synthesis of the Pyrrolidine Ring System by Radical Cyclization

A series of bromo-substituted allyl- and diallyl-substituted sulfonamides have been found to undergo free radical cyclization when treated with tri-n-butyltin hydride in the presence of AIBN.The regiochemical course of the cyclization depends on the nature of the substituent groups attached to the ?-bond.The stereoelectronic factors governing the cyclization reaction of these N-allylsulfonamides are even more stringent than those which occur with the simple 5-hexenyl system.This is probably related to the shorter C-N bond distance which promotes the 5-exo trigcyclization pathway.The present method provides an attractive entry to the preparation of pyrrolidines from easily available N-(2-bromoethyl)-N-allyl- and N-(2-bromopropenyl)-N-allylsulfonamides.The method represents a clear-cut example of the use of hetero-substituted radicals in C-C bond-forming processes.

Radical cyclization as an approach toward the synthesis of pyrrolidines

Free radical cyclizations of several bromo allyl and diallyl substituted sulfonamides are described. The regiochemical course of these cyclizations depend on the nature of the substituent groups attached to the π-bond.