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11.
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
12.
Synthesis and binding studies of new bis-calix[4]arenes containing aromatic and heteroaromatic units
A series of new bis-calix[4]arenes containing different aromatic and heteroaromatic moieties have been synthesized. The complexing behavior of these bis-calix[4]arenes have been studied towards different metal ions and it has been found that these bis-calix[4]arenes bind silver ions selectively over other metal ions. The complexation has been studied by liquid-liquid extraction and by NMR and IR spectroscopy. 相似文献
13.
Synthesis and rearrangement of bicyclo(4.3.0) - 2β - hydroxy - 2α - vinyl - 1β - methyl - 8 - oxo - Δ6 - nonene was observed to yield a transannular reaction product tricycio - (6.3.0.01,8) - 2 - methyl - 8α - hydroxy - 4 - oxo - Δ2 - undecene 16. Spectral evidence supports the assigned structure. 相似文献
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S Chandrasekhar G Chandrashekar B Nagendra Babu K Vijeender K Venkatram Reddy 《Tetrahedron letters》2004,45(28):5497-5499
A facile synthesis of symmetrical and unsymmetrical ethers is achieved by reductive coupling of carbonyl compounds with alkoxysilanes. This reaction is performed using inert polymethylhydrosiloxane as the hydride source and B(C6F5)3 as the catalytic activator of the PMHS. 相似文献
19.
A simple and efficient method for the preparation of isonucleoside 7 is described. The preparation of 1,4-anhydroxylitol 4, a key intermediate, is described by intramolecular cyclization of (2S,3R,4R)-3,5-dibenzyloxypentan-1,2,4-triol 3 using diethyl carbonate and NaH. 相似文献
20.
N. Seshu Babu 《Tetrahedron letters》2007,48(43):7642-7645
The intermolecular hydroamination of vinyl arene derivatives has been efficiently carried out using a tungstophosphoric acid (TPA) catalyst under solvent free and mild reaction conditions. The present protocol provides an environmentally benign, easy to handle and highly active solid acid catalyst for hydroamination of vinyl arenes. The catalyst yields both hydroamination and hydroarylation products and the selectivity mostly depends on the reaction conditions. 相似文献