847547-27-7

Upstream product

• 1122-54-9 methyl (4-pyridyl) ketone 
• 65032-27-1 ethynylmagnesium chloride 
• 74-86-2 acetylene 
• 1066-54-2 trimethylsilylacetylene 
• 4301-14-8 acetylenemagnesium bromide 

Relevant academic research and scientific papers

Further chemistry of ruthenium alkenyl acetylide complexes: Routes to allenylidene complexes via a series of electrophilic addition reactions

The methyl substituents in the cationic allenylidene complexes trans-[Ru{C=C=C(Me)R}Cl(dppe)2]OTf ([1a?f]OTf) are readily deprotonated to give the corresponding alkenyl acetylide complexes trans-[Ru{C=CC(=CH2)R}Cl(dppe)2] (3; R = Me (a), Ph (b), cC5H10 (c), 4-MeS-C6H4 (d), cC4H3S (e), cC5H4N (f)). Similar chemistry is also observed from [Ru{C=C=C(Me)Ph}(dppe)Cp*]PF6 ([2b]PF6) and [Ru{C=C=C(Me)(4-MeS-C6H4)}(dppe)Cp*]PF6([2b]PF6), chosen to broaden the reaction scope, giving [Ru{C= CC(=CH2)Ph}(dppe)Cp*] (4b) and [Ru{C=C=C(CH2)(4-MeS-C6H4)}(dppe)Cp*] (4d). In turn, reactions of 3b,d and 4b,d with the [BF4]? salt of the electrophilic tritylium [CPh3]+ cation give the functionalized allenylidene complexes trans-[Ru{C=C=C(CH2CPh3)R}Cl(dppe)2]BF4 ([5b,d]BF4) and [Ru{C=C=C(CH2CPh3)R}(dppe)Cp*]BF4 ([6b,d]BF4) formed by addition of the electrophile to the remote vinylic carbon (C(δ)). Although trans-[Ru{C=C=C(CH2CPh3)Me}Cl(dppe)2]BF4 ([5a]BF4) could not be successfully purified from reactions of 3a with [CPh3]BF4, deprotonation of the crude product gave the Zaitsev vinyl product trans-[Ru{C=CC(=CHCPh3)Me}Cl(dppe)2] (7a) in good yield. The initial cycloheptatrienyl adducts formed from reactions of 3b,d and 4b,d with the tropylium salt [C7H7]BF4 undergo a ring-contraction process in chloroform solutions upon exposure to air, to give the styrene-like products trans-[Ru{C=C=C(R)C(H)=CHPh}Cl(dppe)2]BF4 ([10b,d]BF4) and [Ru{C=C= C(R)C(H)=CHPh}(dppe)Cp*]BF4 ([11b,d]BF4), through what is believed to be a radical mechanism mediated by triplet oxygen.

Alkynylation of aldehydes and ketones using the Bu4NOH/H 2O/DMSO catalytic composition: A wide-scope methodology

The Favorsky reaction of a wide range of aldehydes and ketones with alkynes has been implemented under mild conditions (5-20 C). Using a Bu 4NOH/H2O/DMSO catalytic system, propargylic alcohols are formed cleanly in 39-93% (mostly 72-93%) yields and with ca. 100% selectivity. The method is suitable for aliphatic, aromatic, and heteroaromatic aldehydes and ketones, and for aliphatic, aromatic, and functionalized acetylenes. Thus, this represents the most general and efficient protocol to achieve the Favorsky reaction. Copyright

Improved synthesis of tertiary propargyl alcohols by the Favorskii reaction of alkyl aryl (hetaryl) ketones with acetylene

Alkyl aryl (hetaryl) ketones react with acetylene under atmospheric pressure in the superbasic system KOH-EtOH-H2O-DMSO at 10-15 C (2 h) to give the corresponding tertiary propargyl alcohols in up to 91% yield. The procedure requires no large excess of KOH and low-boiling inflammable solvents, produces few wastes, and is safe and convenient on the laboratory scale; there are no limitations for its large-scale application.

An enzymatic toolbox for the kinetic resolution of 2-(Pyridin-x-yl)but-3- yn-2-ols and tertiary cyanohydrins

The kinetic resolution of a series of acetates of tertiary alcohols bearing a nitrogen substituent has been studied by using several recombinant carboxyl esterases and variants thereof expressed in E. coli. Most of the enzymes were active in the conversion of these tertiary alcohols and excellent enantioselectivities were achieved in the synthesis of three 2-(pyridin-x-yl)but-3-yn-2-ols with the nitrogen atom in the pyridine ring in the 2′-, 3′-, and 4′-positions. The resolution of tertiary cyanohydrins proved to be more difficult as the enantioselectivity of the enzymes was generally lower. Nevertheless, (S)-1-cyano-2,2,2-trifluoro-1- phenylethyl acetate was obtained with 99% ee. The results show that the limited substrate range of the individual enzymes in the synthesis of a series of tertiary alcohols can be efficiently overcome by using a combination of different enzymes.

Synthesis of alkyne derivatives of a novel triazolopyrazine as A 2A adenosine receptor antagonists

A novel [1,2,4]triazolo[1,5-a]pyrazine core was synthesized and coupled with terminal acetylenes. The structure-activity relationship of the alkynes from this novel template was studied for their in vitro and in vivo adenosine A2A receptor antagonism. Selected compounds from this series were shown to have potent in vitro and in vivo activities against adenosine A 2A receptor. Compound 12, in particular, was found to be orally active at 3 mg/kg in both a mouse catalepsy model and a 6-hydroxydopamine- lesioned rat model.