手性螺环骨架硼烷催化酮的不对称硅氢化反应（英文）

受阻路易斯酸碱对(frustrated Lewis pairs, FLPs)是目前合成化学的前沿挑战性研究领域之一,为非金属催化的氢化和Piers-type硅氢化反应提供了非常有效的途径.近年来,相关研究取得了重要的研究进展,但是相应的不对称反应发展比较缓慢.缺乏高效、高选择性的手性催化剂仍然是制约这一领域快速发展的重要因素.手性螺环是配体设计中的优势骨架.基于前期所发展的联萘骨架手性FLP催化剂及其在不对称催化氢化和硅氢化反应的应用,设计并合成了基于手性螺环骨架的手性双烯,通过与HB(C_6F_5)_2的硼氢化反应原位制备了新型手性硼烷路易斯酸.利用其与三叔丁基膦形成的手性受阻路易斯酸碱对催化剂,成功地实现了简单酮的不对称Piers-type硅氢化反应,反应的对映选择性最高可达90%.     

手性二烯作为“配体”的无金属不对称氢化反应

不对称催化氢化反应通常需要过渡金属参与,直到最近几年"Frustrated Lewis Pairs(FLPs)"概念的提出及其能够实现氢气活化,为发展无金属参与的不对称氢化反应提供了机遇.但由于光学纯的FLP催化剂难以制备,目前其在不对称催化氢化反应中的应用非常少,发展高对映选择性的非金属催化的氢化反应仍十分具有挑战性.中国科学院化学研究所杜海峰等基于手性烯烃作为"酉己体"的新策略,利用烯烃的原位硼氢化反应,发展了新颖的手性FLP     

“受阻路易斯酸碱对”活化小分子反应研究进展

"受阻路易斯酸碱对(FLP)"是最近十几年提出的一个崭新的化学理论.由于其独特的化学特性,受阻路易斯酸碱对在非金属催化体系中占据了一席重要的位置.受阻路易斯酸碱对具有活化小分子的特征,包括氢气、烯烃、炔烃、二氧化碳、环醚、硅烷等在内的小分子都可以利用受阻路易斯酸碱对体系进行活化,这为发展主族元素参与的催化反应打开了新思路.综述了受阻路易斯酸碱对的结构和反应特征,并介绍了近年来关于受阻路易斯酸碱对催化活化小分子的反应.     

“受阻”路易斯酸碱对催化氢化反应的研究进展

"受阻"路易斯酸碱对(FLPs)催化氢化反应是当前催化加氢领域的研究热点之一.该类反应具有环境友好、无重金属残留等特点,具有潜在的工业化应用前景.根据底物类别,对近几年"受阻"路易斯酸碱对在催化氢化领域的研究进展进行简要评述,并对FLPs不对称催化氢化进行简单介绍.     

手性受阻路易斯酸碱对催化的烯醇硅醚不对称氢化反应

正J.Am.Chem.Soc.2014,136,12261~12264受阻路易斯酸碱对(FLPs)化学的发展为非金属催化氢化提供了崭新的途径,一系列不饱和化合物的催化氢化反应相继实现,但相应的不催对称催化氢化仍处于起步阶段,反应的对映选择性低于90%,同时底物也仅限于亚胺和喹啉两类化合物.因此发展高对映选择性的不对称催化新体系是这个领域中亟待解决的重要挑战性难题之一.中国     

亚胺的不对称催化氢化研究进展

手性胺化合物是重要的有机合成中间体,在农药、医药及精细化学品合成中有着广泛的应用,而通过亚胺的不对称催化氢化是获得手性胺化合物最直接、最高效的方法之一.近二十年来,亚胺的不对称催化氢化取得了重大进展.各种高活性、高立体选择性的手性配体和催化剂被设计并合成出来,各种新的不对称催化方法和策略被发展并得到成功应用,各种特殊及挑战性亚胺底物的氢化取得重要突破.然而亚胺的不对称催化氢化反应依然存在着诸如反应活性低、底物范围窄、反应条件苛刻、催化剂不易回收等问题.因此,发展更加高效、高选择性、环境友好的不对称氢化方法,是未来亚胺的不对称催化氢化发展的方向.从亚胺的类型入手,就环状和非环状的亚胺的不对称催化氢化反应的研究进展进行综述.     

金属催化的不对称氢化反应研究进展与展望

手性过渡金属络合物催化的不对称氢化反应是合成光学活性化合物的重要方法. 本文从手性配体及手性催化剂、不对称催化新反应、新方法和新策略三个方面简要评述新世纪以来过渡金属催化的不对称氢化反应研究领域的新进展. 从新世纪初至今, 手性单磷配体得到了复兴, 出现了如MonoPhos、SiPhos、DpenPhos等高效单齿亚磷酰胺酯配体; 磷原子手性(P-手性)配体也得到了快速发展, 如BenzP*、ZhanPhos、TriFer等已成为新的高效手性双膦配体; 螺环骨架手性配体成为新世纪手性配体设计合成的亮点, 除了SiPhos、SIPHOX、SpinPHOX等高效手性螺环配体外, 手性螺环吡啶胺基磷配体SpiroPAP的铱催化剂成为目前最高效的分子催化剂. 不对称催化氢化新反应研究也取得了突破, 如非保护烯胺、杂芳环化合物及N-H亚胺的氢化等反应都实现了高对映选择性. 自组装手性催化剂、树枝状手性催化剂、铁磁性纳米负载的可回收手性催化剂, 以及“混合”配体手性催化剂等新方法和新策略也在不对称催化氢化反应中得到了应用. 然而, 手性过渡金属络合物催化的不对称氢化研究仍然充满挑战, 也期待新的突破.     

全固体受阻路易斯酸碱对的设计与构建

正受阻路易斯酸碱对(Frustrated Lewis Pairs,FLPs)是均相催化领域一类新型的非金属有机催化剂,因其在氢气和二氧化碳等惰性小分子的活化转化方面具有极高的活性,近年来引起了学术界的高度关注~(1–4)。FLPs一般由分子内或分子间的一对路易斯酸和路易斯碱构成,但由于空间配位受阻使这两个位点不能形成传统的路易斯酸碱化合物,从而表现出一些特殊的化学性质和催化活性。但是,均相FLPs具有制备过程复杂、稳定性     

基于稀土金属路易斯酸碱对化学的研究进展

近年来,利用稀土金属作为路易斯酸,与主族路易斯碱组合的路易斯酸碱对得到了开发.这类酸碱对组合通过路易斯酸与路易斯碱协同作用,从而实现底物的活化,展示了与传统稀土金属配合物不同的活化模式.其可以与氢气反应,断裂非极性的氢-氢键;也能够与羰基类、重氮类及叠氮类等不饱和小分子反应,得到一系列结构独特的稀土金属配合物.同时这类路易斯酸碱对也可以用于催化极性烯烃聚合反应、二氧化碳硅氢化还原反应中,展现出优异的催化性能.综述了上述研究结果,并对该领域的发展趋势和前景进行了展望.     

失配的Lewis对:非金属催化氢化的新策略

“失配的Lewis对”(Frustrated Lewis Pairs,FLPs)作为有机化学领域的新概念,在非金属活化H2,CO2和NH3等小分子方面的研究和应用格外引人注目.以“失配的Lewis对”为催化剂,直接以氢气作为氢源,非金属催化氢化还原醛、烯胺、亚胺、腈和二氧化碳等获得了很好的结果.手性“失配的Lewis对”(Chiral Frustrated Lewis Pairs,Chiral FLPs)在不对称催化氢化还原亚胺的反应中也呈现出较高的光学选择性,产物胺的对映体过量最高达83％ ee.综述了近几年“失配的Lewis对”在非金属催化氢化研究领域的进展情况.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.