259218-91-2

Upstream product

• 133886-40-5 N-tosyl-N-allylpropargylamine 
• 67-64-1 acetone 
• 55022-46-3 4-methyl-N-prop-2-ynylbenzenesulfonamide 
• 98-59-9 p-toluenesulfonyl chloride 

Downstream Products

• 1380420-83-6 5-((N-allyl-4-methylphenyl)sulfonamido)-2-methylpent-3-yn-2-yl acetate 

Relevant academic research and scientific papers

Asymmetric Reductive and Alkynylative Heck Bicyclization of Enynes to Access Conformationally Restricted Aza[3.1.0]bicycles

Conformationally restricted azabicycles are becoming increasingly important in medicinal research. Asymmetric Heck bicyclization of enynes proceeds to give medicinally useful aza[3.1.0] and aza[4.1.0] bicycles with excellent enantioselectivity. The key organopalladium species after bicyclization can be trapped by silanes and terminal alkynes.

Hydrogenative metathesis of enynes via piano-stool ruthenium carbene complexes formed by alkyne gem-hydrogenation

The only recently discovered gem-hydrogenation of internal alkynes is a fundamentally new transformation, in which both H atoms of dihydrogen are transferred to the same C atom of a triple bond while the other position transforms into a discrete metal carbene complex. [Cp?RuCl]4 is presently the catalyst of choice: the resulting piano-stool ruthenium carbenes can engage a tethered alkene into either cyclopropanation or metathesis, and a prototypical example of such a reactive intermediate with an olefin ligated to the ruthenium center has been isolated and characterized by X-ray diffraction. It is the substitution pattern of the olefin that determines whether metathesis or cyclopropanation takes place: a systematic survey using alkenes of largely different character in combination with a computational study of the mechanism at the local coupled cluster level of theory allowed the preparative results to be sorted and an intuitive model with predictive power to be proposed. This model links the course of the reaction to the polarization of the double bond as well as to the stability of the secondary carbene complex formed, if metathesis were to take place. The first application of "hydrogenative metathesis"to the total synthesis of sinularones E and F concurred with this interpretation and allowed the proposed structure of these marine natural products to be confirmed. During this synthesis, it was found that gem-hydrogenation also provides opportunities for C-H functionalization. Moreover, silylated alkynes are shown to participate well in hydrogenative metathesis, which opens a new entry into valuable allylsilane building blocks. Crystallographic evidence suggests that the polarized [Ru-Cl] bond of the catalyst interacts with the neighboring R3Si group. Since attractive interligand Cl/R3Si contacts had already previously been invoked to explain the outcome of various ruthenium-catalyzed reactions, including trans-hydrosilylation, the experimental confirmation provided herein has implications beyond the present case.

Hydrogenative Cyclopropanation and Hydrogenative Metathesis

The unusual geminal hydrogenation of a propargyl alcohol derivative with [CpXRuCl] as the catalyst entails formation of pianostool ruthenium carbenes in the first place; these reactive intermediates can be intercepted with tethered alkenes to give either cyclopropanes or cyclic olefins as the result of a formal metathesis event. The course of the reaction is critically dependent on the substitution pattern of the alkene trap.

Annelated Cyclobutanes by Fe-Catalyzed Cycloisomerization of Enyne Acetates

Cationic Fe complexes of the general type [(Ph3P)2Fe(CO)(NO)]X (X=BF4, BArF4) catalyze the redox-neutral cycloisomerization of 1,6- and 1,7-enyneacetates to afford bicyclic cyclobutanes under mild conditions in good yields and diastereoselectivities.

Practical cobalt carbonyl catalysis in the thermal Pauson-Khand reaction: Efficiency enhancement using Lewis bases

In this report we have shown that the commercially available CO2(CO)8 and CO4(CO)12, and enyne-CO2(CO)6 complexes, are sufficiently effective in catalyzing the Pauson - Khand reaction under

Catalyst precursors for the catalytic Pauson-Khand reaction

Dicobalt hexacarbonyl complexes of enynes serve as Co2(CO)8 surrogates for the intramolecular Pauson-Khand cycloaddition. Enynes with polar functional groups allow for easy separation of the catalyst cyclopentenone by-product (acid o