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991.
Kohei Fuchibe 《Tetrahedron》2006,62(49):11304-11310
An enantioselective [3+2]-type cycloaddition of allenylstannane and α-imino ester was developed. Synthetic utility of the 4-stannyldehydroproline ester intermediate was demonstrated: iodine oxidation and Stille coupling reaction of the intermediate afforded optically active 4-iodo- and 4-aryldehydroproline esters in good yields and in high ees, respectively. 相似文献
992.
N,N-Dialkyl(3,3,3-trifluoro-1-propynyl)amines were prepared by a three-step procedure starting from commercially available 2,2,3,3,3-pentafluoropropanol. The reactions of these trifluoromethylated ynamines with some electrophiles, such as aldehydes, halogens or N-halosuccinimides (NXS), were investigated. The fluorinated ynamines reacted with aldehydes in the presence of a catalytic amount of Lewis acid to provide the corresponding α-(trifluoromethyl)-α,β-unsaturated amides in good to excellent yields with high Z-stereoselectivity. These ynamines reacted with molecular bomine to give, after treatment with sodium hydrogen carbonate, N,N-dialkyl-2-bromo-3,3,3-trifluoropropanamides in good yields. The reaction with an equimolecular amount of NXS in aqueous acetonitrile also gave the corresponding 2-halo-3,3,3-trifluoropropanamides in good to excellent yields. On the other hand, the reaction of the ynamine with NXS in anhydrous acetonitrile led to the formation of the addition products in high yields. Upon treating the addition products with an equimolecular amount of NX′S in aqueous acetonitrile, the corresponding 2,2-dihalo(X,X′)-3,3,3-trifluoropropanamides were produced in nearly quantitative yields. 相似文献
993.
A convergent method for synthesizing 6/n/6/6 (n=7, 8) tetracyclic ether system via two-rings construction of the central n/6 ring system was developed. The key steps of the present synthesis involve a ring-closing metathesis reaction for the construction of the seven- and eight-membered rings, and reductive etherification for the tetrahydropyrans. Unification of the two fragments through acetal formation, followed by regioselective cleavage of the acetal using TMSCN/TMSOTf in the presence of 2,6-di-tert-butyl-4-methylpyridine, afforded the α-cyano ether, of which the nitrile group was manipulated to give the precursors of the ring-closing reactions. 相似文献
994.
Haiming Wang 《Tetrahedron》2006,62(17):3985-3988
A temperature-controlled highly selective dimerization of α-methylstyrene to produce 2,4-diphenyl-4-methyl-1-pentene and 1,1,3-trimethyl-3-phenylindan was catalyzed by Brönsted acidic ionic liquid [Hmim]+BF4−. At 60 °C, 2,4-diphenyl-4-methyl-1-pentene was formed in 93% selectivity with >92% conversion under a solvent-free condition while 1,1,3-trimethyl-3-phenylindan could be obtained in 100% selectivity when the reaction temperature was increased to 170 °C. The ionic liquid [Hmim]+BF4− could be reused with almost no loss of activity. 相似文献
995.
Matthias Bierenstiel 《Tetrahedron》2005,61(21):4911-4917
The NaBrO3/NaHSO3 reagent is one of the few oxidizing agents that chemoselectively oxidizes vicinal diols to α-hydroxy ketones with little overoxidation to the corresponding vicinal-dione or dicarboxylic acid. Oxidation reactions performed with this reagent showed strong pH dependence. cis-Vicinal diols reacted faster than trans-vicinal diols to the α-hydroxy ketone product. Hydroxy functional groups at axial ring positions were more readily oxidized than equatorial hydroxy groups. The application of the NaBrO3/NaHSO3 reagent for the chemoselective oxidation of vicinal diols was limited to simple systems and failed with more complex monosaccharide compounds probably due to acid catalyzed dehydrogenation reactions. Despite the simple reaction set-up and good selectivity towards the α-hydroxy ketone product, the actual oxidation reaction mechanism is highly complex and postulated to involve at least six different equilibria with a plethora of bromine containing species. A possible oxidation reaction mechanism is discussed. 相似文献
996.
An efficient two-step synthesis of p-toluenesulfonic acid salts of optically active 3-amino-3-alkyl-2-oxetanones is reported that involves cyclization of N-Boc-α-alkylserines under Mitsunobu reaction conditions followed by deprotection of the amino group with trifluoroacetic acid in the presence of anhydrous p-toluenesulfonic acid. 相似文献
997.
(R)-4-Hydroxymethyl-2-phenyl-4,5-dihydrooxazol-4-ylmethyl acetate was efficiently obtained by lipase-catalyzed asymmetrization of the prochiral diol. (R)-4-Hydroxymethyl-2-phenyl-4,5-dihydrooxazol-4-ylmethyl acetate was converted to (R)-2-(hydroxymethyl)glutamic acid and a synthetic intermediate of (−)-deoxydysibetaine. 相似文献
998.
Tatjana Jeremic 《Tetrahedron》2005,61(7):1871-1883
The synthesis and conformational analysis of two Aib-containing cyclic hexapeptides, cyclo(Gly-Aib-Leu-Aib-Phe-Aib) 1 and cyclo(Leu-Aib-Phe-Gly-Aib-Aib) 2, is described. The linear precursors of 1 and 2 were prepared using solution phase techniques, and the cyclization efficiency of three different coupling reagents (HATU, PyAOP, DEPC) was examined. The success of the cyclization was found to be reagent dependent. Solid-state conformational analysis of 1 and 2 was performed by X-ray crystallography and has revealed some unusual features as all three Aib residues of 1 assume nonhelical conformations. Furthermore, the residue Aib4 adopts an extended conformation (?=−175.9(3)°, ψ=+178.6(2)°), which is, to the best of our knowledge, the first observation of an Aib residue adopting an extended conformation in a cyclopeptide. The structure of 1 is also a rare example in which an Aib residue occupies the (i+1) position of a type II′ β-turn, stabilized by a bifurcated hydrogen bond. The cyclic peptide 2 adopts a more regular conformation in the solid state, consisting of two fused β-turns of type I/I′, stabilized by a pair of intramolecular hydrogen bonds. In addition, the conformational study of the cyclic peptide 1 in DMSO-d6 by NMR spectroscopy and molecular dynamics simulations revealed a structure, which is very similar to its structure in the crystalline state. 相似文献
999.
Mairi GibsonJonathan M. Goodman Louis J. FarrugiaRichard C. Hartley 《Tetrahedron letters》2003,44(14):2841-2844
A 1,3-dithiane displaces tosylate by a 5-exo-tet cyclisation to give a bicyclic sulfonium salt. Nucleophilic attack on this 4-thia-7a-thioniaperhydroindene by azide ions kinetically favours opening to give a nine-membered ring α-azidosulfide, but 2-(3′-azidopropyl)-1,3-dithiane is the thermodynamic product from B3LYP/6-31G** calculations. A similar sulfonium salt generated from 2-(3′-hydroxypropyl)-1,3-dithiane with thionyl chloride rearranges to 2-(3′-chloropropyl)-1,3-dithiane. Azide ion displacement of the primary alkyl chloride is then faster than [1.4] sulfanyl participation from the thioacetal. An α-chlorosulfide derived from diphenyldithioacetal does not rearrange but undergoes direct displacement to give an α-azidosulfide. 相似文献
1000.
1-Unsubstituted 3-alkyl/aryl-3-amino-1H,3H-quinoline-2,4-diones react with 1-substituted and 1,1-disubstituted ureas in boiling acetic acid to give 2,6-dihydro-imidazo[1,5-c]quinazoline-3,5-diones. In contrast, the reaction of these amines with nitrourea in dioxane affords novel 3-alkyl/aryl-3-ureido-1H,3H-quinoline-2,4-diones or 9b-hydroxy-3a-alkyl/aryl-3,3a,5,9b-tetrahydro-1H-imidazo[4,5-c]quinoline-2,4-diones, which can smoothly be dehydrated to 3a-alkyl/aryl-3,3a-dihydro-5H-imidazo[4,5-c]quinoline-2,4-diones. All three types of products can be converted to 2,6-dihydro-imidazo[1,5-c]quinazoline-3,5-diones by refluxing in acetic acid. 相似文献