43055-47-6

Upstream product

• 16640-68-9 cyanomethylene triphenylphosphorane 
• 603-35-0 triphenylphosphine 
• 74-88-4 methyl iodide 
• 43055-42-1 (Cyano-methyl-methyl)-triphenyl-phosphonium; bromide 

Downstream Products

• 26157-51-7 (Z)-2-methyl-3-phenyl-2-propenenitrile 
• 53587-72-7 (E)-2-methyl-3-phenylacrylonitrile 
• 53244-20-5 2-methyl-6-phenylhexanenitrile 
• 1582271-55-3 4-benzyl-2-methyl-2,3-allenenitrile 
• 252357-37-2 (R,S)-4-(tert-butyloxycarbonylamino)-6,6-difluoro-3-oxo-2-triphenylphosphoranylidene-hexanenitrile 
• 252357-48-5 (+/-)-4-(N-benzyloxycarbonyl-amino)-6,6-difluoro-3-oxo-2-triphenylphosphoranylidene-hexanenitrile 
• 19724-44-8 2-oxopropanenitrile 2,4-dinitrophenylhydrazone 
• 1197-33-7 2-methyl-3-phenyl-acrylonitrile 

Relevant academic research and scientific papers

Stereoselective olefination of N-sulfonyl imines with stabilized phosphonium ylides for the synthesis of electron-deficient alkenes

An unprecedented protocol has been developed for thestereoselective synthesis of structurally diverse electron-deficient alkenes in moderate to excellent yields from readily accessible N-sulfonyl imines and stabilized phosphonium ylides. Significantly, the olefination reaction of N-sulfonylimines with nitrile-stabilized phosphonium ylides affords an array of α,β-unsaturated nitriles with high Z selectivity, and the reactions with ester-, amide-, and ketone-stabilized phosphonium ylides afford α,β-unsaturated esters, amides, and ketones with high E selectivity, respectively. Spectroscopic analysis of the reaction mixtures and trapping of the intermediates allow plausible mechanisms to be proposed. Initialimine/ylide addition leads to the formation of betaines that cyclize to form 1,2-azaphosphetanes that subsequently eliminate iminophosphoranes to yield alkenes. For the synthesis of electron-deficient 1,2-disubstituted alkenes, the presence of an electron-withdrawing group in the betaine allows rapid interconversion between its two diastereomers through proton transfer. The Z/E selectivity for alkene synthesis is determined by the different rates at which the two betaine diastereomers form the corresponding 1,2-azaphosphetane diastereomers. In contrast, the Z/E selectivity for the synthesis of electron-deficient trisubstituted alkenes originates from the diastereoselective addition of stabilized phosphonium ylides to N-sulfonyl imines.

SNTHESIS AND "ANOMERIZATION" OF C-GLYCOSYL COMPUNDS RELATED TO SOME HETEROCYCLIC NATURAL PRODUCTS

Reaction of 2,3-O-isopropylidene-D-ribofuranose (13) with the stabilized Wittig reagents Ph3P=C(Me)CO2Me (14) and Ph3P=C(Me)CN (15) gave olefinic products which, upon treatment with dilute base, afforded the corresponding anhydro sugars having the β-D-anomer configuration excusively.Treatment of these kinetic products with a strong base did not affect the ester obtained from 14, but the nitrile from 15 gave a β-to-α-anomer ratio at equilibrium of 4:1.Reaction of 13 with Ph3P=CHCOMe led directly to a 7:3 mixture of β- and α-D anomers, and this ratio was changed to 1:4 upon prolonged exposure to base.Treatment of 4,6-O-ethylidene-D-glucopyranose with the Wittig reagent Ph3P=CHCOCH2CO2Et led directly to a 1:1 mixture of the anomers of the anhydro sugar in which a β-keto ester residue is attached at the (original) anomeric center.This ratio of anomeric forms coud not be changed by treatment with base, but the ethylidene-protecting group could be removed, and the resulting tetrol tritylated at the primary position.