96133-27-6

Upstream product

• 62845-83-4 4-(tert-butyl)cyclohex-1-en-1-yl diethyl phosphate 
• 22955-77-7 methyl 1-indanone-2-carboxylate 
• 10442-39-4 tetra-n-butylammonium cyanide 
• 98-53-3 4-tercbutyl-cyclohexanone 
• 96133-26-5 1-triethylgermyl-4-t-butylcyclohexene 
• 62082-37-5 hydrazone of 4-tert-butylcyclohexane 
• 77412-96-5 1-trifluoromethanesulfonyloxy-4-t-butylcyclohexene 
• 119061-98-2 1-(tributylstannyl)-4-tert-butylcyclohexene 
• 63031-67-4 4-(1,1-dimethylethyl)cyclohexen-1-yltrimethylsilane 

Downstream Products

• 33800-81-6 4-(tert-butyl)-1-vinyl-1-cyclohexene 
• 2228-98-0 4-tert-butylcylohexene 
• 61187-40-4 4-(tert-butyl)cyclohex-1-enecarbaldehyde 
• 273937-88-5 1-(4-tert-butylcyclohex-1-enyl)-2-methylbenzene 
• 1062572-98-8 diethyl N-(4-tert-butyl-cyclohex-1-en-1-yl-carbonyl)-α-aminobenzyl-phosphonate 
• 1235993-93-7 N-methyl-N-methoxy-4-tert-butyl-cyclohex-1-enecarboxamide 
• 33061-20-0 1-(4-tert-butylcyclohex-1-en-1-yl)-4-methoxybenzene 
• 35906-02-6 4-tert-buthyl-1-cyclohexene-1-carboxamide 
• 67001-73-4 4-(tert-butyl)cyclohex-1-ene-1-carboxylic acid 
• 1397263-74-9 4-tert-butylcyclohexenyl carboxylic acid phenyl ester 
• 23022-33-5 4-tert-butyl-1-cyclohexene-1-carboxylic acid ethyl ester 
• 22173-19-9 4-tert-butyl-1-cyclohexene-1-carboxylic acid methyl ester 

Relevant academic research and scientific papers

Amino- and azidocarbonylation of iodoalkenes

Iodoalkenes, available from ketones via their hydrazones, underwent palladium-catalysed azidocarbonylation. Depending on the structure of the acyl azides, consecutive hydrolysis toward corresponding primary amides was observed. ‘Direct’ aminocarbonylation

Nickel-Catalyzed Conversion of Enol Triflates into Alkenyl Halides

A Ni-catalyzed halogenation of enol triflates was developed and it enables the synthesis of a broad range of alkenyl iodides, bromides, and chlorides under mild reaction conditions. The reaction utilizes inexpensive, bench-stable Ni(OAc)2?4 H2O as a precatalyst and proceeds at room temperature in the presence of sub-stoichiometric Zn and either 1,5-cyclooctadiene or 4-(N,N-dimethylamino)pyridine.

Ruthenium-catalyzed transformation of aryl and alkenyl triflates to halides

Aryl triflates were transformed to aryl bromides/iodides simply by treating them with LiBr/NaI and [Cp*Ru(MeCN)3]OTf. The ruthenium complex also catalyzed the transformation of alkenyl sulfonates and phosphates to alkenyl halides under mild conditions. Aryl and alkenyl triflates undergo oxidative addition to a ruthenium(II) complex to form η'1- arylruthenium and 1-ruthenacyclopropene intermediates, respectively, which are transformed to the corresponding halides.

Photochemical generation of six- and five-membered cyclic vinyl cations

The photochemical solvolyses of 4-tert-butylcyclohex-1-enyl(phenyl)iodonium tetrafluoroborate (1) and cyclopent-1-enyl(phenyl)iodonium tetrafluoroborate (2) in methanol yield vinylic ethers and vinylic cycloalkenyliodobenzenes and cycloalkenylbenzene, which are the trapping products of the geometrically destabilized C6-ring and C5-ring vinyl cation with the solvent and with the leaving group iodobenzene. Iodonium salt 2 also yields an allylic ether and allylic cyclopentenyliodobenzenes and cyclopentenyl-benzene, which are the trapping products of the C5-ring allylic cation produced from the C5-ring vinyl cation by a hydride shift in a typical carbocationic rearrangement.

Michael addition-elimination mechanism for nucleophilic substitution reaction of cycloalkenyl iodonium salts and selectivity of 1,2-hydrogen shift in cycloalkylidene intermediate

(Chemical Equation Presented) Reactions of cyclohexenyl and cyclopentenyl iodonium salts with cyanide ion in chloroform give cyanide substitution products of allylic and vinylic forms. Deuterium-labeling experiments show that the allylic product is formed via the Michael addition of cyanide to the vinylic iodonium salt, followed by elimination of the iodonio group and 1,2-hydrogen shift in the 2-cyanocycloalkylidene intermediate. The hydrogen shift preferentially occurs from the methylene rather than the methine β-position of the carbene, and the selectivity is rationalized by the DFT calculations. The Michael reaction was also observed in the reaction of cyclopentenyliodonium salt with acetate ion in chloroform. The vinylic substitution products are ascribed to the ligand-coupling (via λ3-iodane) and elimination-addition (via cyclohexyne) pathways.

Michael addition of cyanide to cyclohex-1-enyliodonium salts

Reaction of 4-substituted cyclohex-1-enyliodonium salt with cyanide in chloroform produces three isomeric cyanocyclohexenes, ipso and two cine products. Deuterium labeling experiments showed that the allylic cine product is formed via the Michael addition of cyanide, followed by elimination of the iodonio group and a 1,2-H shift.

α-Vinylation of 1,3-Dicarbonyl Compounds with Alkenyl(aryl)iodonium Tetrafluoroborates: Effects of Substituents on the Aromatic Ring and of Radical Inhibitors

Direct α-vinylations of enolate anions derived from 1,3-dicarbonyl compounds with 4-teri-butyl-1- cyclohexenyl(aryl)iodonium 2 and 1-cyclopentenyl(aryl)iodonium tetrafluoroborates 3 are reported. Frequently, α-phenylations compete with the vinylations in the reaction of 1,3-dicarbonyl compounds with alkenyl(phenyl)iodonium salts 2a and 3a. Use of alkenyl(p-methoxyphenyl)iodonium salts 2b and 3b, however, leads to selective α-vinylation at the expense of the competing arylation of 1,3-dicarbonyl compounds. Use of an efficient aryl radical trap, 1,1-diphenylethylene, inhibits radical-induced decomposition of the alkenyl(aryl)iodonium salts, thereby improving the yields of α-vinylations of enolate anions derived from 1,3-dicarbonyl compounds.

The Reaction of Vinyl Phosphates with Iodotrimethylsilane: Synthesis of Vinyl Iodides from Ketones

A new method for preparation of vinyl iodides from ketones is described, based on the reaction of vinyl phosphates with iodotrimethylsilane.

REACTIONS OF VINYLSILANES WITH LEWIS ACID-ACTIVATED IODOSYLBENZENE: STEREOSPECIFIC SYNTHESIS OF VINYLIODONIUM TETRAFLUOROBORATES AND THEIR REACTIONS AS HIGHLY ACTIVATED VINYL HALIDES

Alkenyl(phenyl)iodonium tetrafluoroborates 3 were synthesized from alkenylsilanes 1 by the reaction with iodosylbenzene and boron trifluoride-diethyl ether or triethyloxonium tetrafluoroborate.The reaction proceeds stereospecifically with retention of configuration of 1.X-ray diffraction analysis of (4-tert-butylcyclohexenyl)phenyliodonium tetrafluoroborate (3b) revealed the highly ionic structure with the distorted T-shape arrangement.Iodonium salts 3 behave like the highly activated species of vinyl iodides due to the high leaving ability of the iodine(III) substituents.Thus, a variety of substituted olefins including α-cyano and α-nitro olefins, vinyl sulfides, vinyl halides and α,β-unsaturated esters, were synthesized from 3 under mild conditions.A ligand coupling mechanism via the formation of 10-I-3 intermediate 27 containing a copper(III) ligand is proposed for the substitutions of 3 with nucleophiles.

VINYLIODONIUM SALTS: THEIR STEREOSPECIFIC SYNTHESIS AND REACTIONS AS THE ACTIVATED VINYL HALIDES

Vinyliodonium salts 2 were synthesized from vinylsilanes 1 by the reaction with iodosylbenzene and triethyloxonium tetrafluoroborate.The reaction occurs stereospecifically with retention of configuration.Vinyliodonium salts 2 are highly effective as the activated species of vinyl iodides.Thus, a variety of substituted olefins including α-cyano and α-nitro olefins, vinyl sulfides, vinyl halides, and α,β-unsaturated esters, were prepared from 2 under mild reaction conditions.