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81.
An efficient route for the regio- and stereoselective ring opening of N-tosylaziridines with zinc dihalides (ZnX2, X = Cl, Br, I) is described. Depending on the solvent and Zn(II) halide, β-halo amines or imidazolines are obtained selectively in good to excellent yields. 相似文献
82.
Surendra K Krishnaveni NS Reddy MA Nageswar YV Rao KR 《The Journal of organic chemistry》2003,68(5):2058-2059
A mild and efficient oxidation of alcohols with o-iodoxybenzoic acid (IBX) catalyzed by beta-cyclodextrin in a water/acetone mixture (86:14) has been developed. A series of alcohols were oxidized at room temperature in excellent yields. 相似文献
83.
The regio– and stereoselective synthesis of the keto-esters 20 and 22 are described, the latter being a potential intermediate to several diterpenes. The key steps involve the Diels-Alder cycloaddition between the benzocycloheptenone 5 and cyclopentadiene followed by a regioselective functionalisation of the adduct 6. A remarkable reversal of regioselectivity was observed during oxymercuration of the unsymmetric double bond in 6 and its reduced product 11 leading to 8 and 12 which were subsequently transformed to 20 and 22 respectively. 相似文献
84.
Venkatapuram Padmavathi Boggu Jagan Mohan Reddy Adivireddy Padmaja 《Journal of heterocyclic chemistry》2005,42(2):333-335
A new class of 3,4‐disubstituted pyrroles has been prepared by the reaction of 1‐aroyl‐2‐arylsul‐fonylethenes and 1,2‐diarylsulfonylethenes with tosyl methyl isocyanide. 相似文献
85.
Treatment of the bis(allylsulfoximine)titanium complexes derived from the beta-methyl-substituted acyclic allylic sulfoximines 13a and 13b with aldehydes gave with high selectivities the corresponding sulfoximine-substituted homoallylic alcohols which were isolated as the silyl ethers 15a-h. Methylation of sulfoximines 15a-h afforded the aminosulfoxonium salts 5a-h which upon treatment with LiN(H)tBu gave in high yields the enantio- and diastereomerically pure silyl-substituted 2,3-dihydrofurans 4a-h. Treatment of the titanium complexes derived from the cyclic allylic sulfoximines 17a, 17b, and ent-17c with p-MeOC(6)H(4)CHO delivered with high selectivities the corresponding sulfoximine-substituted cyclic homoallylic alcohols which were isolated as the silyl ethers 18a, 18b, and ent-18c, respectively. Methylation of sulfoximines 18a, 18b, and ent-18c furnished the aminosulfoxonium salts 8a, 8b, and ent-8c, respectively, whose treatment with LiN(H)t-Bu gave the enantio- and diastereomerically pure fused bicyclic 2,3-dihydrofurans 6a, 6b, and ent-6c, respectively, in good yields. It is proposed that the 1-alkenyl aminosulfoxonium salts 5a-h, 8a, 8b, and ent-8c react with the base under alpha-elimination and formation of the acyclic and cyclic beta-silyloxy alkylidene carbenes 2a-h, 7a, 7b, and ent-7c, respectively, which then undergo a 1,5-O,Si-bond insertion and 1,2-silyl migration. The cyclic aminosulfoxonium salts 8a, 8b, and ent-8c upon treatment with 1,8-diazabicyclo[5.4.0]-7-undecene did not undergo an alpha-elimination but suffered a novel migratory cyclization with formation of the enantio- and diastereomerically pure bicyclic tetrahydrofurans 9a, 9b, and ent-9c, respectively. It is proposed that the 1-alkenyl sulfoxonium salts 8a, 8b, and ent-8c are isomerized to the allylic aminosulfoxonium salts 10a, 10b, and ent-10c, respectively, which then suffer an intramolecular substitution of the (dimethylamino)sulfoxonium group by the silyloxy group followed by a desilylation. The syntheses of the 2,3-dihydrofurans 4a-h, 6a, and 6b and of the tetrahydrofurans 9a and 9b are accompanied by the formation of sulfinamide 16 of >or=98% ee, which can be converted via sulfoxide 28 of >or=98% to the starting sulfoximine 11 of >or=98% ee. 相似文献
86.
The o-, m-, and p-phenylene bis(1,3-dioxolanium) dications (4-6) and 2,4,6-triphenylene tris(1,3-dioxolanium) trication (7) have been prepared by the ionization of the corresponding 2-methoxyethyl benzoates in FSO(3)H or CF(3)SO(3)H at 40 and 60 degrees C, respectively. The charge delocalization in these carbocations was probed by (13)C NMR chemical shifts and substantiated by GIAO/DFT calculations. Relatively less charge is delocalized into the aromatic ring of the carbotrication 7. The rotational barrier around the C(+)-Ar bond for carbodications 4 and 5 was also estimated to be 8-10 kcal/mol. 相似文献
87.
TDDFT calculations confirm a controversial proposal by DiMagno and co-workers that ruffling distortions, by themselves, do not bring about sizable red shifts in the electronic absorption spectra of "simple" nontransition-metal porphyrins. We now report that the same also holds for saddling distortions. The situation is more complex for transition metal porphyrins. For example, ruffling does bring about strong red shifts in the electronic spectra of nickel porphyrins because of a specific metal(d)-porphyrin(pi) orbital interaction. 相似文献
88.
J.S. Yadav B.V. Subba Reddy K.V. Raghavendra Rao G.G.K.S. Narayana Kumar 《Tetrahedron letters》2007,48(31):5573-5576
Indoles undergo smooth alkylation with propargylic alcohols in the presence of 10 mol % of scandium triflate under mild conditions to produce 3-propargylated indoles in excellent yields with high selectivity. 相似文献
89.
T. Ashok Reddy M. Srinivasan 《Journal of polymer science. Part A, Polymer chemistry》1987,25(11):2987-3003
Several polyesters containing thiaxanthone rings were prepared from 2,7-dichloroformylthiaxanthone-5,5′-dioxide ( IVa ), 2,8-dichloroformylthiaxanthone-5,5′-dioxide ( IVb ), and bisphenols by solution polycondensation. The 2,8-diethoxycarbonylthiaxanthone-5,5′-dioxide ( V ) was prepared and characterized by spectral methods to confirm the formation of 2,8-thiaxanthonedicarboxylic acid-5,5′-dioxide ( IVb ). Prior to polymer synthesis two model compounds,2,7-diphenoxycarbonylthiaxanthone-5,5′-dioxide (MDE-1) and 2,8-diphenoxycarbonylthiaxanthone-5,5′-dioxide (MDE-2), were synthesized and characterized by spectral methods. The polyesters were obtained in 62–78% yield and had inherent viscosities in the range 0.42–0.90 dL/g. The effect of thiaxanthone rings on solubility, crystallinity, and thermal stability of the polyesters are also discussed. The polyesters have decomposition temperatures in the range 372–438°C. 相似文献
90.
An efficient and mild method for the reduction of aromatic nitro and azido groups on solid support using Al/NiCl2·6H2O and Al/NH4Cl is described. This solid phase reduction technique has been applied towards the synthesis of DNA binding pyrrolo[2,1-c][1,4]benzodiazepine antitumour antibiotics. 相似文献