Enantioselective Synthesis of Acyclic Orthogonally Functionalized Compounds Bearing a Quaternary Stereocenter Using Chiral Ammonium Salt Catalysis

We herein report an asymmetric protocol to access a series of orthogonally functionalized acyclic chiral target molecules containing a quaternary stereogenic center by carrying out the enantioselective α-alkylation of novel orthogonally functionalized dioxolane-containing cyanoacetates under chiral ammonium salt catalysis. By using just 1 mol % of Maruoka's spirocyclic ammonium salt catalysts enantioselectivities up to e.r.=97.5 : 2.5 could be achieved and further functional group manipulations of the products were carried out as well.     

对称季铵碱的烷基链长度对草酸电还原反应的影响

研究了四种不同烷基链长度的对称季铵碱对草酸电还原制备乙醛酸反应的影响。线性扫描测试考察了添加剂对铅电极上阴极反应的影响,结果表明对称季铵碱在电极表面的吸附对析氢反应的抑制程度大于其对草酸电还原反应的抑制程度,且随着对称季铵碱中烷基链长度的增加,添加剂抑制析氢反应效果更明显。计时安培法的结果证明添加剂可影响草酸向电极表面的扩散,随着对称季铵碱中烷基链长度的增加,草酸的扩散系数呈现出先增加后减小的趋势。恒流电解实验结果表明,添加剂能有效提高草酸电还原反应的电流效率,且提高效果随对称季铵碱所含烷基链长度的增加而增强。因此,添加剂的吸附对阴极表面析氢反应的抑制作用是草酸电还原反应电流效率提高的主要原因。本研究表明,四丁基氢氧化铵为添加剂时,草酸还原为乙醛酸的电流效率最高。     

K_2CdSnS_4的溶剂热合成与晶体结构(英文)

利用溶剂热法合成了层状硫代锡(Ⅲ)酸镉(Ⅱ)化合物K2CdSnS4。单晶X-射线衍射分析结果表明,化合物属单斜晶系,C2/c空间群,a=1.102 1(5)nm,b=1.103 0(5)nm,c=1.515 1(10)nm,α=90°,β=100.416(12)°,γ=90°,V=1.811 4(17)nm3,Z=8,Dc=3.209 g·cm-3,Mr=437.60,μ=6.853 mm-1,F(000)=1 600,λ=0.071 073 nm,R=0.104 2,wR=0.200 8。该化合物由类金刚烷[Cd2Sn2S10]8-结构单元互相连接形成层状结构。紫外-可见漫反射光谱研究表明,化合物为半导体,带隙为2.2 eV。     

季铵盐类阳离子单体的合成工艺研究进展

对季铵盐类阳离子单体的合成工艺及结构改性研究进展进行了综述。基于季铵盐类阳离子单体的基本结构与性质,从合成反应基本历程及代表性制备工艺方法出发,介绍了二烯丙基季铵盐类、丙烯酰胺烷基季铵盐类和丙烯酰胺烷基季铵盐类三类最为重要的季铵盐阳离子单体的合成、聚合及结构改性最新研究进展,指出了已有研究工作的特色与不足,并认为开发高质量丙烯酰胺烷基季铵盐类单体及聚合物产品以及高纯度质量稳定的阳离子单体制备新工艺是今后应努力的方向。     

同系物季铵盐离子液体阳离子的离子交换色谱法分析

建立了离子交换色谱-直接电导检测法分离测定3种同系物季铵盐离子液体阳离子(四甲基铵、四乙基铵和四丙基铵阳离子)的方法。采用磺酸型阳离子交换色谱柱,以乙二胺-柠檬酸-乙腈为淋洗液,考察了淋洗液种类、浓度及色谱柱温度对3种阳离子保留的影响。并根据测定对象不同,调整乙二胺浓度及乙腈含量以改善分离效果。淋洗液中增加乙腈含量,可明显缩短四丙基铵阳离子的保留时间,并改善其色谱峰形。季铵阳离子同系物的保留符合碳数规律。优化的色谱条件为:流速1.0 mL/min,色谱柱温度40℃;以0.02 mmol/L乙二胺-0.12 mmol/L柠檬酸(pH 4.0)为淋洗液分离测定四甲基铵;以0.2 mmol/L乙二胺-0.4 mmol/L柠檬酸-1%乙腈(pH 4.0)为淋洗液分离测定四乙基铵和四丙基铵。所测阳离子的检出限(S/N=3)分别为0.015,0.22,1.88 mg/L,相对标准偏差(n=5)均小于2.3%。将方法应用于表面活性剂和实验室合成的离子液体的分析,加标回收率为99%~104%。本方法简单、准确、可靠,具有良好的实用性。     

A Conjugate Addition Approach to Diazo-Containing Scaffolds with β Quaternary Centers

Structurally complex diazo-containing scaffolds are formed by conjugate addition to vinyl diazonium salts. The electrophile, a little studied α-diazonium-α,β-unsaturated carbonyl compound, is formed at low temperature under mild conditions by treating β-hydroxy-α-diazo carbonyls with Sc(OTf)₃. Conjugate addition occurs selectively at the 3-position of indole to give α-diazo-β-indole carbonyls, and enoxy silanes react to give 2-diazo-1,4-dicarbonyl products. These reactions result in the formation of tertiary and quaternary centers, and give products that would be otherwise difficult to form. Importantly, the diazo functional group is retained within the molecule for future manipulation. Treating an α-diazo ester indole addition product with Rh₂(OAc)₄ caused a rearrangement to occur to give a 2-(1H-indol-3-yl)-2-enoate. In the case of diazo ketone compounds, this shift occurred spontaneously on prolonged exposure to the Lewis acidic reaction conditions.     

镉汞四元硒化物K8Cd2.79Hg9.21Se16和Rb4Hg3.04Cd2.96Se8的溶剂热合成及表征

利用溶剂热法合成了2种含镉汞的二维(2D)四元硒化物K8Cd2.79Hg9.21Se16(1)和Rb4Hg3.04Cd2.96Se8 (2)。单晶X射线衍射分析表明,化合物1为正交晶系,空间群为Pbcn,a=1.082 71(17) nm,b=0.678 73(10) nm,c=1.415 0(2) nm,Z=1;化合物2为正交晶系,空间群为Ibam,a=0.640 72(10) nm,b=1.160 25(16) nm,c=1.452 0(2) nm,Z=2。化合物1中含有八元环Cd2Hg2Se4和六元环CdHg2Se3阴离子层(Cd2.79Hg9.21Se16)n8n-;化合物2中含有八元环Cd2(Cd/Hg)2Se4及四元环CdHgSe2和(Cd/Hg)2Se2阴离子层(Hg3.04Cd2.96Se8)n4n-。对这2种化合物进行了扫描电镜和能谱分析、粉末X射线衍射、差示扫描量热分析、固体-可见漫反射光谱和荧光性质等表征。     

Enantioselective Catalytic Aldehyde α‐Alkylation/Semipinacol Rearrangement: Construction of α‐Quaternary‐δ‐Carbonyl Cycloketones and Total Synthesis of (+)‐Cerapicol

An enantioselective aldehyde α‐alkylation/semipinacol rearrangement was achieved through organo‐SOMO catalysis. The catalytically generated enamine radical cation serves as a carbon radical electrophile that can stereoselectively add to the alkene of an allylic alcohol and initiate ensuing ring‐expansion of cyclopropanol or cyclobutanol. This tandem reaction enables the production of a wide range of nonracemic functionalizable α‐quaternary‐δ‐carbonyl cycloketones in high yields and excellent enantioselectivity from simple aldehydes and allylic alcohols. As a key step, the intramolecular reaction was also successfully applied in the asymmetric total synthesis of (+)‐cerapicol.     

Cu‐Catalyzed Diastereo‐ and Enantioselective Reactions of γ,γ‐Disubstituted Allyldiboron Compounds with Ketones

A catalytic diastereo‐ and enantioselective method for the preparation of complex tertiary homoallylic alcohols containing a vicinal quaternary carbon stereogenic center and a versatile alkenylboronic ester is disclosed. Transformations are promoted by 5 mol % of a readily available copper catalyst bearing a bulky monodentate phosphoramidite ligand, which is essential for attaining both high dr and er. Reactions proceed with a wide variety of ketones and allylic 1,1‐diboronate reagents, which enables the efficient preparation of diverse array of molecular scaffolds.