75712-94-6

Upstream product

• 3355-31-5 1-chloro-3-phenyl-2-propyne 
• 2568-65-2 N,N-dimethyl-3-phenyl-2-propyn-1-amine 
• 73845-05-3 N-methanesulfonyl benzylideneamine 
• 205582-30-5 [(dimethylamino)ethyl]triphenylphosphonium bromide 
• 536-74-3 phenylacetylene 
• 64-17-5 ethanol 
• 21331-80-6 [2-(dimethylamino)ethyl]triphenylphosphonium bromide 
• 100-52-7 benzaldehyde 
• 42817-44-7 (E)-N,N-dimethyl-3-phenylprop-2-en-1-amine 

Downstream Products

• 75712-95-7 cis-cinnamyldimethyl-(3-phenylprop-2-ynyl)ammonium bromide 
• 1581720-14-0 (2S,3S)-methyl 2-(dimethylamino)-3-phenylpent-4-enoate 
• 1581720-07-1 (2S,3S)-N-benzyl-2-(dimethylamino)-3-phenylpent-4-enamide 
• 38846-06-9 3-dimethylamino-1,4-diphenylhex-5-en-1-yne 
• 38846-06-9 3-dimethylamino-1,4-diphenylhex-5-en-1-yne 

Relevant academic research and scientific papers

Diastereoselective [2,3]-Sigmatropic Rearrangement of N-Allyl Ammonium Ylides

A rapid and diastereoselective method was developed for the [2,3]-sigmatropic rearrangement of N-Allyl ammonium ylides, affording products in up to 95percent isolated yields and up to 97:3 dr; most of the desired products were formed within 1 minute. For

Tandem Palladium and Isothiourea Relay Catalysis: Enantioselective Synthesis of α-Amino Acid Derivatives via Allylic Amination and [2,3]-Sigmatropic Rearrangement

A tandem relay catalytic protocol using both Pd and isothiourea catalysis has been developed for the enantioselective synthesis of α-amino acid derivatives containing two stereogenic centers from readily accessible N,N-disubstituted glycine aryl esters and allylic phosphates. The optimized process uses a bench-stable succinimide-based Pd precatalyst (FurCat) to promote Pd-catalyzed allylic ammonium salt generation from the allylic phosphate and the glycine aryl ester. Subsequent in situ enantioselective [2,3]-sigmatropic rearrangement catalyzed by the isothiourea benzotetramisole forms syn-α-amino acid derivatives with high diastereo- and enantioselectivity. This methodology is most effective using 4-nitrophenylglycine esters and tolerates a variety of substituted cinnamic and styrenyl allylic ethyl phosphates. The use of challenging unsymmetrical N-allyl-N-methylglycine esters is also tolerated under the catalytic relay conditions without compromising stereoselectivity.

Cobalt-catalyzed (Z)-selective semihydrogenation of alkynes with molecular hydrogen

Cobalt-catalyzed highly (Z)-selective semihydrogenation of alkynes using molecular H2 was developed using commercially available and cheap cobalt precursors. A variety of (Z)-alkenes were obtained in moderate to excellent selectivities [(Z)-alkene/(E)-alkene/alkane ratio up to >99 : 1 : 1] and it was found that the readily available ethylenediamine ligand is crucial in determining the selectivity.

An isothiourea-catalyzed asymmetric [2,3]-rearrangement of allylic ammonium ylides

Benzotetramisole promotes the catalytic asymmetric [2,3]-rearrangement of allylic quaternary ammonium salts (either isolated or prepared in situ from p-nitrophenyl bromoacetate and the corresponding allylic amine), generating syn-α-amino acid derivatives with excellent diastereo- and enantioselectivity (up to >95:5 dr; up to >99% ee).

Tunable stereoselective alkene synthesis by treatment of activated imines with nonstabilized phosphonium ylides

A broad range of readily accessible N-sulfonyl imines undergo olefination reaction with nonstabilized phosphonium ylides under mild conditions to afford an array of both Z- and E-isomers of 1,2-disubstituted alkenes, allylic alcohols, and allylic amines in good yields and with greater than 991 stereoselectivity.

Chain-length- and solvent-dependent intramolecular proton transfer in styrene-amine exciplexes

The photochemical and photophysical behavior of several ((N,N-dimethylamino)alkyl)styrenes in which the amino group is attached to the styrene α- or β-carbon by a methyl, ethyl, propyl, or butyl polymethylene chain has been investigated. Efficient intramolecular addition of an aminomethyl C-H to styrene is observed in nonpolar solvents for the (aminoethyl)styrenes, and addition of an aminomethylene C-H is observed for the (aminobutyl)styrenes. However, the (aminoethyl)- and (aminopropyl)styrenes do not undergo intramolecular addition reactions. Both the reactive and unreactive (aminoalkyl)styrenes form fluorescent singlet exciplexes in nonpolar and polar solvents. The resuls of exciplex and product quenching by an added primary amine indicate that the fluorescent exciplex is an intermediate in the addition reactions of the (aminoalkyl)styrenes. Activation parameters for both exciplex formation and exciplex proton transfer have been determined. Highly regioselective intramolecular proton transfer is proposed to occur via least motion pathways from the lowest energy folded conformations of the singlet exciplex intermediates in nonpolar solvents. The solvent dependence of exciplex proton transfer, fluorescence, intersystem crossing, and nonradiative decay is attributed to a change in exciplex conformation from folded in nonpolar solvents to extended in solvents more polar than diethyl ether.

ANOMALOUS STEREOCHEMISTRY IN THE WITTIG REACTION INDUCED BY NUCLEOPHILIC GROUPS IN THE PHOSPHONIUM YLIDE

Reaction of ylides from 3-9 with benzaldehyde show that carboxylate and oxido functionalities proximate to the ylide center promote anomalously high E stereoselectivity in alkene formation.Through the use of α-deuterated ylides 12-14, an internal "trans-selective Wittig" mechanism was ruled out as a principal source of exaggerated E alkene production.

Base Catalysed Rearrangements involving Ylide Intermediates. Part 1. The Rearrangements of Diallyl- and Allylpropynyl-ammonium Cations

The base catalysed rearrangements of diallylammonium cations and allylpropynylammonium cations are described.In most cases, the major product arises by a symmetry-allowed sigmatropic rearrangement of the intermediate ylide.The minor products can be regarded as being derived by homolysis of the ylide into a radical pair followed by recombination.