155335-41-4

Upstream product

• 98-59-9 p-toluenesulfonyl chloride 
• 62773-87-9 N-(2-propenyl)-N-(2,2-dimethoxyethyl)amine 
• 58754-95-3 N-(2,2-dimethoxyethyl)-p-toluenesulfonamide 
• 106-95-6 allyl bromide 
• 4431-85-0 bromodimethoxymethane 
• 50487-71-3 4-methyl-N-(2-propenyl)benzenesulfonamide 
• 68-12-2 N,N-dimethyl-formamide 

Downstream Products

• 1159092-28-0 N-(2-(allyltosylamino)ethylidene)benzohydrazide 
• 155335-43-6 Methyl (E)-4--2-butenoate 
• 204574-78-7 4-methyl-N-[(diphenylhydrazono)ethyl]-N-(2-propenyl)benzenesulfonamide 
• 361459-74-7 4-methyl-N-(2-oxoethyl)-N-2-propen-1-ylbenzenesulfonamide 

Relevant academic research and scientific papers

Diversity-oriented synthesis of hydrazine-derived compounds from amino isocyanates generated in situ

Behind the mask: Nitrogen-substituted isocyanates are rare and their synthetic potential is virtually untapped. Simple masked precursors can form amphoteric amino isocyanate intermediates in situ, and allows the synthesis of complex hydrazine derivatives upon addition with amines. This reactivity was used in a cascade substitution/hydroamination sequence, and in the assembly of azadipeptide analogues. Copyright

Synthesis of small and large fused bicyclic compounds by tandem dienyne ring-closing metathesis

(Equation Presented). A tandem ring-closing metathesis reaction using ruthenium catalyst was carried out to synthesize various fused bicyclic compounds containing both small and large rings. Fast ring-closure of the small ring and slow ring-closure of the large ring resulted in the formation of only one isomer. Further manipulation such as the Diels-Alder reaction was carried out to prepare a complex molecule containing multiple rings of different sizes.

Hydrazides as tunable reagents for alkene hydroamination and aminocarbonylation

(Chemical Equation Presented) Benzoic hydrazides (R = Ph), which are remarkably bench and thermally stable reagents (often up to 230°C), afford intramolecular hydroamination products upon heating at high temperatures (120-235°C). A concerted Cope-type hydroamination event, followed by a hydrazide-mediated proton transfer step of the hydrazinium ylide intermediate, is proposed and supported by DFT calculations. In contrast, a simple modification of the reagent structure (R = Ot-Bu or NH2) favors the formation of aminocarbonylation products at 200°C, and the latter reaction is shown to be stereospecific. Copyright

Radical cyclization in heterocycle synthesis. Part 13: Sulfanyl radical addition-cyclization of oxime ethers and hydrazones connected with alkenes for synthesis of cyclic β-amino acids

A combination of sulfanyl radical addition-cyclization of the oxime ethers and hydrazones connected with alkenes and subsequent conversion of a phenylsulfanylmethyl group to a carboxyl group provides a novel method for the construction of the cyclic β-amino acids. Upon treatment with thiophenol in the presence of AIBN, the oxime ethers and hydrazones smoothly underwent sulfanyl radical addition-cyclization to give the 2-(phenylsulfanylmethyl)cycloalkylamine. This method was successfully applied to the practical synthesis of 2-aminocyclopentanecarboxylic acid and 4-amino-3-pyrrolidinecarboxylic acid.

Reductive Cyclization of Ketones Tethered to Activated Olefins Mediated by Magnesium in Methanol

The reductive cyclization of various ketones tethered to activated olefins such as α,β-unsaturated esters, nitriles, sulfoxides, and sulfides mediated by magnesium in dry methanol in the presence of mercuric chloride.When traeted with magnesium in dry methanol at -23 deg C all of the ketones except nitrile 9 (42percent) and 5-oxa-8-keto-2-enoate 5 (13percent) gave excellent yields (79-98percent) of mono- and bicyclic alcohol products resulting from carbon-carbon bond formation between the β-carbon of the activated olefin and the carbonyl carbon.The reaction was accelerated by the catalytic amount of mercuric chloride, although the stereoselectivity was not affected by the catalyst.For all the substrates except 8-keto-2-enoate 3 and 5-aza-8-keto-2-enoate 6, the configuration of the major product was trans between the hydroxy and (methoxycarbonyl)methyl groups.The product isomer ratios were independent of the substrate geometry (E or Z).In contrast to the ketones, aldehydes tethered to α,β-unsaturated esters gave products of simple reduction of the double bond and/or saturated alcohols instead of the cyclized products.When the reaction temperature was lowered, the yields of cyclized product were significantly affected by the production of appreciable amounts of saturated product, but the stereoselectivity was not improved.Under the same reaction conditions α,β-unsaturated sulfoxide 16 gave deoxygenated sulfide 18 (85percent) as the major product along with a small amount (9percent) of cyclized product 19t.In contrast, sulfone 17 underwent desulfonylation instead of cyclization to give olefin 20 (54percent).With excess magnesium (15 equiv), however, α,β-unsaturated sulfoxide 16 gave cyclized sulfide 19t (95percent) via deoxygenated sulfide 18.Both 16Z and 16E afforded product 19t as a single isomer.It is suggested that the reductive cyclization of the α,β-unsaturated esters and nitriles proceed by means of nucleophilic attack of a β-carbon radical anion, formed by initial electron transfer from magnesium metal to the activated olefin, on the carbonyl group.The cyclization of the α,β-unsaturated sulfide proceeds by nucleophilic attack of the ketyl on the olefinic double bond.