91158-83-7

Upstream product

• 77412-96-5 1-trifluoromethanesulfonyloxy-4-t-butylcyclohexene 
• 250643-77-7 tris(2-(trimethylsilyl)ethynyl)indium 
• 23525-05-5 1-bromo-4-(tert-butyl)cyclohex-1-ene 
• 1066-54-2 trimethylsilylacetylene 
• 81353-38-0 (trimethylsilylethynyl)tributyltin 
• 183598-09-6 4-tert-butyl-1-(trimethylsilylethynyl)cyclohexan-1-ol 
• 16035-50-0 trimethyl(trimethylstannanylethynyl)silane 

Downstream Products

• 100319-42-4 4-(tert-butyl)-1-ethynylcyclohex-1-ene 

Relevant academic research and scientific papers

Complementary iron(II)-catalyzed oxidative transformations of allenes with different oxidants

Substituent- and oxidant-dependent transformations of allenes are described. Given the profound influence of the substituent on the reactivity of allenes, the subtle differences in allene structures are manifested in the formation of diverse products when reacted with different electrophiles/oxidants. In general, reactions of nonsilylated allenes involve an allylic cation intermediate by forming a C-O bond, at the sp-hybridized C2, with either DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone) or TBHP (tert-butyl hydroperoxide), along with FeCl2·4 H2O (10 mol %). In contrast, silylated allenes favor the formation of propargylic cation intermediates by transferring the allenic hydride to the oxidant, thus generating 1,3-enynes (E1 product) or propargylic THBP ethers (SN1 product). The formation of these different putative cationic intermediates from nonsilylated and silylated allenes is strongly supported by DFT calculations. Profound impact: Iron(II)-catalyzed transformations of allenes induced by either DDQ or tBuOOH depend on the substituent on the allenes. Nonsilylated and silylated allenes show complementary reactivity upon exposure to DDQ and tBuOOH in the presence of an iron(II) catalyst. Nonsilylated allenes incorporate the oxidant at the sp-hybridized carbon, whereas the silylated allenes generate 1,4-dehydrogenated 1,3-enynes. DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone.

Efficient synthesis of functionalized furans via ruthenium-catalyzed cyclization of epoxyalkyne derivatives

Ruthenium catalyst TpRuPPh3(CH3CN)2Cl is found to effect the cyclization of epoxyalkynes to furans in the presence of Et3N. The reactions worked well for various epoxyalkynes with suitable oxygen and nitrogen functionalities with low loading of catalyst. It failed with disubstituted epoxyalkynes. The mechanism was elucidated by a deuterium labeling experiment that suggested that the mechanism involved a ruthenium-vinylidenium intermediate.

Atom-efficient metal-catalyzed cross-coupling reaction of indium organometallics with organic electrophiles

The novel metal-catalyzed cross-coupling reaction of indium organometallics with organic electrophiles is described. Triorganoindium compounds (R3In) containing alkyl, vinyl, aryl, and alkynyl groups are efficiently prepared from the correspond

Palladium-catalyzed cross-coupling reactions of triorganoindium compounds with vinyl and aryl triflates or iodides

(matrix presented) A novel palladium-catalyzed cross-coupling reaction of organoindium compounds with vinyl and aryl triflates or iodides is described. The reaction proceeds for alkyl-, vinyl-, alkynyl-, and arylindium compounds in excellent yields and high chemoselectivity without any excess of the organometallic. Remarkably, indium organometallics transfer efficiently the three organic groups attached to the metal.

Synthesis of enynes and epoxyenynes by coupling: Use of a new set of catalysts based on Pd-Ag salts

The new couple of catalysts Pd(PPh3)4 and AgI are very efficient for the coupling of vinyltriflates and terminal alkynes in the presence of a bulky amine in dimethylformamide at room temperature. Enynes and epoxyenynes are obtained in good to excellent yields. As illustrated with several examples, a wide variety of functional groups are well tolerated in the described conditions. Silver acetylides have been proposed as intermediate in this reaction.

A new synthesis of trimethylsilyl-substituted enyne and (Z)-enediyne compounds

Trimethylsilyl (TMS)-substituted enynes 9-11, 13-17 and (Z)-enediynes 18 were prepared by dehydration of the TMS-substituted propargyl alcohols 1-8 with polyphosphoric acid trimethylsilyl ester.