Asymmetric Baeyer—Villiger oxidation: control of stereoelectronic demand

The recent development of asymmetric Baeyer—Villiger oxidation of prochiral and racemic ketones is briefly summarized, focusing on the regio- and stereocontrol of the oxidation attained by regulating the stereoelectronic demand in the step of rearrangement of the Criegee intermediate.Based on the report presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1784–1794, September, 2004.     

Synthesis of 1,2-bis(methoxyamino)cycloalkanes from alicyclic 1,2-bis(hydroxyamines)

Derivatives of 1,4-dihydroxypiperazine-2,3-dione were obtained by reaction of cis-1,2-bis(hydroxyamino)cycloalkanes with diethyl oxalate. Their alkylation with CH₂N₂ or Mel afforded 1,4-dimethoxypiperazine-2,3-diones. Hydrolysis of the latter gave 1,2-bis(methoxyamino)cycloalkanes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 925–929, April, 1996.     

The first example of the C-3 alkylation of indoles with cyclopropyl ketones promoted by CeCl3·7H2O/LiI

Indoles undergo smooth alkylation with cyclopropyl ketones in the presence of the CeCl₃·7H₂O/LiI reagent system in refluxing acetonitrile under neutral conditions to produce the corresponding C-3 substituted indole derivatives in good to high yields and with high selectivity. The use of CeCl₃·7H₂O/LiI makes this method simple, convenient, and cost-effective.     

聚合物支载噁唑类化合物在不对称反应中的应用

聚合物支载噁唑类化合物主要包括聚合物支载噁唑烷酮、噁唑啉和硼杂噁唑啉等,其在不对称反应中主要用作手性助剂、手性催化剂及催化剂配体.由于其便于分离提纯、可以回收重复使用且立体选择性没有明显降低等优点在不对称反应中得到了广泛的应用.综述了近年来聚合物支载的噁唑类化合物在不对称反应中的应用     

Reaction of indium ate complexes with allylic compounds. Controlling SN2/SN2′ selectivity by solvents

Vinyl and methylindium ate complexes (indates) were prepared and both the tendency of immigration and regioselectivity toward cinnamyl bromide were investigated. The vinyl group was more preferably transferred than the Me group, giving a regioisomeric mixture of S_N2 and S_N2′ products. The ratio of S_N2/S_N2′ selectivity can be controlled by solvents; in the presence of polar solvents, such as N-butylpyrrolidone (NBP) and THF, the S_N2′ product was mainly obtained, whereas the S_N2 product was selectively prepared in solutions containing hexane. The vinylindium compound, generated by the reaction of allylic-type diindium reagents with imine, was also converted to the corresponding vinyl indate, which was allowed to react with allyl chloride to give a three-component coupling product.     

A Novel Asymmetric ent-Kauranoid Dimer from Isodon enanderianus

ＩｎｔｒｏｄｕｃｔｉｏｎＩｓｏｄｏｎｅｎａｎｄｅｒｉａｎｕｓ (Ｈａｎｄ . Ｍａｚｚ .)Ｈ .Ｗ .Ｌｉ(Ｌａｂｉａｔａｅ) ,ｗｉｄｅｌｙｄｉｓｔｒｉｂｕｔｅｄｉｎｔｈｅｓｏｕｔｈｅｒｎｐａｒｔｓｏｆＹｕｎｎａｎＰｒｏｖｉｎｃｅ ,ｈａｓｂｅｅｎｕｓｅｄｉｎＣｈｉｎｅｓｅｔｒａｄｉｔｉｏｎａｌｆｏｌｋｍｅｄｉｃｉｎｅａｓａｎｔｉ ｉｎｆｌａｍｍａｔｏｒｙａｎｄｄｅｔｏｘｉｆｉｅｄａｇｅｎｔ.1Ｐｒｅｖｉｏｕｓｐｈｙｔｏｃｈｅｍｉｃａｌｉｎｖｅｓｔｉｇａｔｉｏｎｈａｓｓｈｏｗｎｔｈｅｐｒｅｓ ｅｎｃｅｏｆａｓｅｒ…     

光学活性化合物的工业合成

本文介绍了光学活性化合物研究现状及发展趋势。并从技术和经济角度论述了工业合成光学活性化合物的可能性     

Vanadyl salen complexes covalently anchored to an imidazolium ion as catalysts for the cyanosilylation of aldehydes in ionic liquids

Two vanadyl salen complexes having peripheral styryl substituents have been reacted with 1-methyl-3-(3-mercaptopropyl)-imidazolium chloride using azoisobutyronitrile as radical initiator. The resulting compounds contain at the same time a vanadyl salen complex and one imidazolium cation. In agreement with the expectations in view of their structure, these compounds were insoluble in conventional organic solvents, but completely miscible in imidazolium ionic liquids. These vanadyl salen complexes bonded to an imidazolium cation are highly active and reusable catalysts for the cyanosilylation of aldehydes. Moderate enantiomeric excesses were obtained using the chiral version of this complex.