Cyclohex-2-enyl acetate

Azide 190, available through palladium-catalyzed amination of the corresponding cyclohex-2-enyl acetate with azonane, can be sequentially reduced and hydrolyzed to produce amino acid 191 (Equation 11) <2000BML1257>. 

AUylic oxidation. Cyclohexene is oxidized to cyclohex-2-enyl acetate in 75% yield by the reagent at 70° when catalyzed by potassium bromidefea. 8 hr.). The reaction is slow in the absence of a catalyst. Norbomene is unreactive, but bicyclo[3.2.noclene-2 is oxidized rapidly to about an equal mixture of endo- and cxo-bicycIo[3.2.1]oct-3-ene-2-yl acetates. Acyclic olefins or cyclic olefins prone to allylic rearrangement give a complex mixture of allylic acetates. 

Cyclohexene-l-ol, 90 2-Cyclohexenone, 262,484, 511 Cyclohex-2-enyl acetate, 318 Cyclohexylamine, 300 N-Cyclohexylaniline, 377 Cyclohexyl azide, 377 Cyclohexyl bromide, 126 Cyclohexylcarbinol, 192 Cyclohexylcaiboxalhyde, 192 l Cyclohexylcyclohexanol, 52 Cyclohexyldichloroborane, 371 Cyclohexyldimethylamine, 245 N-Cyclohexylhydroxylamine, 80... 

Treatment of bicyclo[4.1.0]heptan-2-ols with perchloric acid in acetic acid caused very clean rearrangement with formation of cyclohept-3-enyl acetates (Table 1). Only in the case of cxo-7-methylbicyclo[4.1.0]heptan-2-ol was the cyclohex-2-enyl acetate the major product probably because the 7-methyl group conferred additional stabilization on the carbocation formed by j0-scission of the outer cyclopropane bond. The same type of reactant could be oxidatively rearranged using pyridinium chlorochromate to afford cyclohepten-4-ones, together with (chloromethyl)cyclohexenes. However, if the chloride in the reagent was replaced with tetrafluoroborate, or if pyridinium chlorochromate was used with silver(I) nitrate, formation of the substituted cyclohexenes was completely suppressed, e.g. formation of 7 from 6, although the reported yields were low. ... 

CAS 1205-42-1 EINECS/ELINCS 214-883-7 Synonyms L-p-Mentha-1(6),8-dien-2-yl acetate cis-2-Methyl-5-(1 -methylvinyl) cyclohex-2-enyl acetate... 

An interesting example of enantioselective catalytic alkylation of carbonyl groups by unqiolung of 7r-allyl palladium complexes has been disclosed recently.A number of chiral ligands have been screened in the palladium-catalyzed alkylation of cyclohex-enyl acetate. The best performing ligand was the monodentate... 

Procedure 3 Resolution of (+)-4-Cyano-4-(3, 4 -dichlorophenyl)cyclohex-l-enyl Acetate (8)... 

When optically active 2-(cyclohex-2-enyl)ethylhydroxylamine (90) [derived from methyl 3-(3,4-methylenedioxy)phenylcyclohex-2-enyl acetate] was heated at 140°C, the A-hydroxyhexahydroindoline 91 was obtained in 83% yield. Reductive cyclization of 91 then gave (-l-)-a -lycorane (92) (Scheme 6). 

To a stirred solution of dimethyl 2-(cyclohex-2-enyl)-2-(3-methylbuta-l,2-dienyl)malonate (100 mg, 0.36 mmol) in 2 mL of acetic acid at 70 C, AuClj (5.5 mg, 0.018 mmol) and AgSbFg (16.4 mg, 0.054 mmol) were added portionwise. The mixture was then stirred for 4 h until total disappearance of the starting material (TLC analysis). The reaction mixture was filtered through a small amount of silica gel and the silica gel was washed with Et20 (5 mL). The combined organic phases were concentrated under vacuum to give the crude product. Purification was carried out by flash chromatography (n-pentane-EtaO, 4 1) on silica gel to yield 75 mg (79%) of pure methyl 3-(cyclohex-2-enyl)-3,6-dihydro-6,6-dimethyl-2-oxo-2Ff-pyran-3-carboxylate. ... 

An elimination-addition mechanism has also been invoked for the nucleophilic substitution of cyclohexenyliodonium salts with acetate ion. For example, the reaction of either the 4- or 5-substituted cyclohex-l-enyl(phenyl)iodonium tetra-fluoroborate (31 or 32 respectively) with tetrabutylainmonium acetate in aprotic solvents gives the ipso and cine acetate substitution products (33 and 34 and vice-versa, respectively) in almost the same ratio (Scheme 23). These results were consistent with an elimination-addition mechanism involving 4-substituted cyclohexyne 35 as a common intermediate. The presence of a cyclohexyne intermediate was confirmed by deuterium labelling and trapping studies leading to [4-l-2]-cycloaddition products. 

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