107442-31-9

Upstream product

• 932-03-6 1-Ethynyl-7-oxa-bicyclo[4.1.0]heptane 
• 100-58-3 phenylmagnesium bromide 
• 87955-56-4 1-(2-phenylethynyl)-7-oxabicyclo<4.1.0>heptane 
• 932-03-6 1-ethynyl-7-oxabicyclo[4.1.0]heptane 
• 591-50-4 iodobenzene 
• 98-80-6 phenylboronic acid 
• 13456-84-3 cyclohex-1-enylethynylbenzene 

Relevant academic research and scientific papers

Stereoselective synthesis of syn-configured α-allenols by rhodium-catalyzed reaction of alkynyl oxiranes with arylboronic acids

(Chemical Equation Presented) A rhodium-catalyzed reaction of alkynyl oxiranes with arylboronic acids affords syn-configured α-allenols with high diastereoselectivity. The reaction is initiated by addition of an arylrhodium(I) species onto the alkyne moie

Stereoselective Traceless Borylation–Allenation of Propargylic Epoxides: Dual Role of the Copper Catalyst

Chiral α-allenols are prepared with high diastereocontrol through an unprecedented and spontaneous β-oxygen elimination of an α-epoxy vinyl boronate. Stochiometric experiments and DFT calculations support a dual role of the copper catalyst, which orchestrates the hydroboration and the syn-elimination step.

Palladium pincer complex catalyzed stannyl and silyl transfer to propargylic substrates: Synthetic scope and mechanism

Pincer complex catalyzed substitution of various propargylic substrates could be achieved using tin- and silicon-based dimetallic reagents to obtain propargyl- and allenylstannanes and silanes. These reactions involving chloride, mesylate, and epoxide substrates could be carried out under mild conditions, and therefore many functionalities (such as COOEt, OR, OH, NR, and NAc) are tolerated. It was shown that pincer catalysts with electron-supplying ligands, such as NCN, SCS, and SeCSe complexes, display the highest catalytic activity. The catalytic substitution of secondary propargyl chlorides and primary propargyl chlorides with electron-withdrawing substituents proceeds with high regioselectivity providing the allenyl product. Opening of the propargyl epoxides takes place with an excellent stereo- and regioselectivity to give stereodefined allenylstannanes. Silylstannanes as dimetallic reagents undergo an exclusive silyl transfer to the propargylic substrate affording allenylsilanes with high regioselectivity. According to our mechanistic studies, the key intermediate of the reaction is an organostannane (or silane)-coordinated pincer complex, which is formed from the dimetallic reagent and the corresponding pincer complex catalyst. DFT modeling studies have shown that the trimethylstannyl functionality is transferred to the propargylic substrate in a single reaction step with high allenyl selectivity. Inspection of the TS structures reveals that the trimethylstannyl group transfer is initiated by the attack of the palladium-tin σ-bond electrons on the propargylic substrate. This is a novel mechanism in palladium chemistry, which is based on the unique topology of the pincer complex catalysts.

Diastereoselective syn or anti opening of propargylic epoxides. Synthesis of α-allenic alcohols

Propargylic epoxides easily react with Grignard reagents and catalytic amounts of copper(I) salt to afford α-allenic alcohols. The reaction is highly diastereoselective and its stereochemical outcome (syn or anti isomer) can be fully controlled. The syn d

COPPER CATALYZED REDUCTIVE METALLATION OF A PROPARGYLIC EPOXIDE TO AN ALLENYL LITHIUM REAGENT

Phenethynyl cyclohexene oxide undergoes a reductive metallation by BuLi and catalytic amount of CuI salt.The resulting allenyl lithium reagent reacts, then, normally, with various electrophiles.

DIASTEREOSELECTIVE SYNTHESIS OF α-ALLENIC ALCOHOLS FROM PROPARGYLIC EPOXIDES

Tha cuprocatalyzed reaction of a Grignard reagent with propargylic epoxides proceed through an addition-elimination mechanism.By changing the reaction conditions, particularly the halogen atom of RMgX it is possible to control the diastereoselectivity of

Organocuprates Containing Dimethyl Sulfoxide Anion as a Nontransferable Ligand

Mixed homocuprates and in which the anion of dimethyl sulfoxide acts as a nontransferable ligand are readily prepared from MeSOCH2Li, alkyl- or aryllithium reagents, and Cu(I) salts.These novel cuprates are useful in the conversions of acid chlorides to ketones, conjugate additions to α,β-unsaturated ketones, SN2' reactions with allylic or propargylic acetates and epoxides, and coupling reactions with primary iodides and tosylates.All of these reactions proceed with selective transfer of the ligand R.From the points of view of cost, availability, and lack of interference with product isolation, the Me2SO anion is an ideal nontransferable ligand.