Reactions ofP-cyanospirophosphoranes with some thiols and alcohols

5-Cyano-2,3,7,8-tetrarnethyl-1,4,6,9-trioxathia-5-phosphaspiro[4.4]nonane reacts with thiols and secondary alcohols only in the presence of Et₃N.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 946–947, May, 1994.     

Reactions of quinones with some aryl phenols and synthesis of new quinone derivatives

In the present study, the reactions of p-chloranil (1a) and 2,3-dichloro-1,4-naphthoquinone (DCNQ) (1b) with some aryl phenols were investigated. The structures of all compounds were characterized using spectroscopic methods (FT-IR, ¹H NMR, ¹³C NMR, and MS) and microanalysis. The electrochemical behaviors of some benzoquinone and naphthoquinone derivatives have also been investigated in unbuffered aprotic solutions.     

二醇及氨基醇类鬼臼毒素衍生物的合成

以天然产物鬼臼毒素(1)为原料，合成了四种二醇及氨基醇类鬼臼毒素衍生物：4-O-乙基表鬼臼苦醇(4)，(1R,2S,3R,4S)-1-3',4',5'-三甲氧基苯基-2-氨甲基-3-羟甲基-4-乙氧基-6,7-亚甲二氧基-1,2,3,4-四氢萘(5)，(1R,2S,3R,4S)-1-3',4',5'-三甲氧基苯基-3-羟甲基-2-氨基-4-乙氧基-6,7-亚甲二氧基-1,2,3,4-四氢萘(6)和4-O-异丙基表鬼臼苦醇(7)。4～7及中间产物8～11都是新化合物。     

Detailed studies on the reduction of aliphatic 3-, 4-, 6-, and 13-oximino esters: Synthesis of novel isomeric amino esters,oximino alcohols,and amino alcohols

The preparation of novel 3-, 4-, 6-, and 13-amino-tetradecanoic acid methyl esters (2a–d) obtained by the reduction of 3-, 4-, 6-, and 13-oximino-tetradecanoic acid methyl esters (1a–d), was investigated. Oximino esters were reduced to afford the corresponding amino esters using NaBH₄–ZrCl₄ reducing system with good yields (58–82%). However, the reduction of oximino esters with LiAlH₄ and BH₃. Tetrahydrofuran gave the corresponding novel 3-, 4-, 6-, and 13-oximino alcohols (3a–d), and 3-, 4-, 6-, and 13-amino alcohols (4a–d) respectively with good chemical yields.     

Synthesis of enantiopure amino alcohols by ring-opening of epoxyalcohols and epoxyethers with ammonia

Arylglycidols and their corresponding ethers undergo regioselective ring-opening with aqueous ammonia in the presence of organic co-solvents (isopropanol or 1,4-dioxane) to afford 1,2-amino alcohols in high yield.     

Asymmetric reduction of ketones with sodium aluminum hydride modified with chiral amino alcohols

Asymmetric reduction of ketones with hydride complexes, which were prepared by in situ modification of NaAlH₄, with various chiral amino alcohols or diamines, was studied. The highest enantioselectivity (up to 93% ee) was achieved using 2-(hydroxydiphenylmethyl)pyrrolidine as a chiral inducing agent.     

Reactions of dichloromaleimides with alcohols,phenols, and thiols

Thiols react with dichloromaleimides in the presence of base to give 2,3-bis[alkyl(aryl)-mercapto]maleimides. Alcohols and phenols in equivalent amounts give 2-alkyl(aryl)oxy-3-chloromaleimides. With two equivalents, phenols give 2,3-bis(aryloxy)maleimides, but alcohols give 2-chloro-3,3-dialkoxysuccinimides in protic solvents and dimeric compounds in aprotic solvents.     

卟啉作为信号传递介质的紫外可见光谱研究

合成了6种氨基酸水杨醛席夫碱(Sal-AA)：Sal-Gly(甘氨酸)、Sal-Phe(苯丙氨酸)、Sal-Arg(精氨酸)、Sal-Tyr(酪氨酸)、Sal-Met(甲硫氨酸)、Sal-Glu(谷氨酸)及其金属铜配合物。并分别在2种不同介质(三氯甲烷和甲醇)中，与四苯基卟啉TPP进行反应，研究了其紫外可见光谱性质，讨论了卟啉作为人工信号转导体系的传递介质，与氨基酸水杨醛席夫碱铜配合物的反应中，实现信号分子铜离子进一步传递的可能性以及溶剂对该信号传递的影响。结果表明，在三氯甲烷为溶剂时，除了Sal-Met的铜配合物之外，其余均能被TPP夺取而形成Metal TPP。而在以甲醇为溶剂时，只有Sal-Gly的铜配合物能被TPP所夺取。     

手性氨基醇在不对称催化中的应用及新进展

综述了手性氨基醇作为配体或催化剂在不对称合成中的应用及最新进展。     

Deallyloxy- and debenzyloxycarbonylation of protected alcohols, amines and thiols via a naphthalene-catalysed lithiation reaction

The naphthalene-catalysed lithiation of Alloc- and Cbz-protected alcohols, amines and thiols in THF at 0 °C led, after quenching with methanol, to the recovery of the free alcohols, amines and thiols in short reaction times and with very good yields. The selectivity for the removal of the Alloc- or the Cbz- group in a polyfunctionalised substrate has been studied. The selective reductive cleavage of a benzylic carbon-oxygen bond was achieved in the presence of an allylic carbon-oxygen or carbon-nitrogen bond. This method represents a great improvement in comparison with the previously reported deprotection procedures by dissolving metals, since it avoids the use of the toxic liquid ammonia and, therefore, the need to perform the reaction at low temperatures.     

Organolithium-induced synthesis of acyclic unsaturated amino alcohols from epoxides of dihydropyrroles and tetrahydropyridines

The alkylative double ring-opening of Bus-protected 2,5-dihydropyrrole epoxides 13 and 29 with organolithiums to give 3-substituted 1-aminobut-3-en-2-ols 13-19 and 30-32 are described. Bus-protected tetrahydropyridine epoxide 38 reacts with organolithiums to give 4-substituted 1-aminobut-4-en-3-ols 39 and tetrahydropyridinol 40.     

Enantioselective alkynylation of aldehydes catalyzed by a camphor sulfonylated amino alcohols titanium(IV) catalyst system

A new titanium(IV) complex has been developed for the effective enantioselective alkynylation of phenylacetylene addition to aldehydes. The titanium(IV) complex was readily prepared in situ from (R)‐C‐(7,7‐dimethyl‐2‐oxo‐bicyclo[2.2.1]hept‐1‐yl)‐(1R,2S)‐N‐(2‐hydroxy‐1,2‐diphenyl‐ethyl)‐methanesulfonamide (1h) and tetraisopropyl titanate [Ti(i‐OPr)₄]. A variety of aromatic aldehydes and α,β‐unsaturated aldehydes were found to be suitable substrates in the presence of the camphor sulfonylated amino alcohol titanium(IV) complex [10 mol% 1h, 40 mol% Ti(i‐OPr)₄]. The desired propargylic alcohols were afforded with high isolated yields (up to 90%) and moderate enantioselectivities (up to 65% ee) under mild conditions. Copyright © 2010 John Wiley & Sons, Ltd.     

光电流谱、光致发光光谱和紫外可见吸收光谱在纳米半导体光电器件研究中的联用

在纳米半导体中由于纳米效应(如量子尺寸效应),其电子结构与块体半导体有所不同。进一步地,当纳米半导体与基底和其他组分结合制成器件后,其性质又受到基底或其他组分的影响,这两点导致了基于纳米半导体的光电器件的性能以及相应表征方法也大不相同。将光电流谱、光致发光光谱和紫外可见吸收光谱三种技术有机地结合起来,可以更好地表征纳米半导体的电子性质和光电性能。本文根据纳米半导体材料与电极的电子性质特点及其测量,结合本课题组前期工作,举例介绍三种谱学方法相结合应用于探究光伏电池和电致发光器件的纳米半导体材料的性能,以及纳米半导体材料表面态的表征。     

N-3 alkylation of uracils with unprotected amino alcohols using the Mitsunobu reaction

During our search for novel CGRP antagonists, we had great difficulty in accessing one of our key motifs. Herein, we communicate how we solved the problem by an unprecedented Mitsunobu alkylation using unprotected amino alcohols.     

Highly enantioselective addition of in situ prepared arylzinc to aldehydes catalyzed by a series of atropisomeric binaphthyl-derived amino alcohols

The direct addition of in situ prepared arylzinc to aldehydes with chiral binaphthyl-derived amino alcohols as catalysts can afford optically active diarylmethanols in high yields and with excellent enantioselectivities (up to 99 % ee, ee = enantiomeric excess). By using a single catalyst, both enantiomers of many pharmaceutically interesting diarylmethanols can be obtained by the proper combination of various arylzinc reagents with different aldehydes; this catalytic system also works well for the phenylation of aliphatic aldehydes to give up to 96 % ee.     

Heterocyclization of amino alcohols into saturated cyclic quaternary ammonium salts

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Reactions of pentachloro-2-nitrobutadiene with some aliphatic and heterocyclic thiols and a crystallographic study

In this study, S-, S,S- and S,O-substituted novel nitrodiene compounds were synthesized. Cyclization products were formed when difunctional nucleophiles were used. The stereoisomerism of a heterocyclic nitrodiene is discussed with the help of XRD studies. The structures of all compounds were characterized by spectroscopic methods (FT-IR, ¹H NMR, ¹³C NMR, ¹⁹F NMR, MS) and microanalysis.