有机小分子催化的不对称Strecker反应研究进展

有机小分子催化的不对称合成反应是目前研究最为活跃的领域之一. 不对称Strecker反应是合成光学活性α-氨基酸衍生物的有效手段. 目前报道的催化不对称Strecker反应的有机催化剂主要有手性胍类、手性(硫)脲衍生物、氮-氧偶极化合物、手性Brønsted酸等, 取得了良好的催化活性和对映选择性. 对各类有机小分子催化剂在有机催化不对称Strecker反应中的应用研究进展, 以及催化剂结构与反应条件对催化活性和不对称诱导作用的影响进行了简要评述.     

双噁唑啉接枝的氨基酸聚合物作为手性催化中心在不对称Henry反应中的应用

通过控制聚合单体L-谷氨酸-γ-乙酯和DL-半胱氨酸以及聚合过程中引发剂与单体的比例,制备了一系列溶解性能不同的氨基酸聚合物.利用其作为负载手性配体的载体,通过双噁唑啉配体上的双键和聚合物上巯基的加成反应,合成了一系列双噁唑啉接枝氨基酸聚合物.将合成的聚合物作为可回收的手性催化剂用于催化不对称Henry反应,反应选择性(e. e.值)在50%～90%之间,产率在67%～95%之间.该催化剂可以循环使用至少7次而不需要经过重新活化.     

N-(6-甲基-2-亚甲基吡啶)-( )-樟脑亚胺体系的不对称烷基化反应

目前,不对称合成光学活性化合物取得了较大进展,不对称合成α-氨基酸、β-氨基醇、α-取代苄胺的报道很多。但是,不对称合成生物碱类物质——α-取代氨甲基吡啶类化合物还未见文献报道,而此类化合物有潜在的应用前景。为此,我们以( )-樟脑为手性试剂     

DpenPhos/Rh(I)催化的β-脱氢氨基酸酯的不对称氢化反应

本文研究了一类结构可调手性单齿亚磷酰胺配体DpenPhos在Rh(I)催化的E和Z型β-脱氢氨基酸酯的不对称催化氢化反应中的应用.经过系统的反应条件和配体结构优化,发现N原子上含有H的亚磷酰胺配体与Rh(I)形成的催化剂通常比N原子上不含H的配体表现出更高的反应活性.在E型β-脱氢氨基酸酯的不对称氢化反应中,催化剂(R,R)-3k/Rh(I)表现突出,可以实现底物的常压催化氢化,取得了92%～96%的对映选择性,催化剂用量可降低至0.2 mol%;对于Z型β-脱氢氨基酸酯的不对称氢化反应,则(R,R)-3l/Rh(I)为最优催化剂,可以获得92%～98%ee值的氢化产物,特别是对于β-芳基取代衍生物的氢化反应,相应氢化产物的ee值可以达到96%～98%.该类催化剂为天然或非天然光学活性β氨基酸的合成提供了一个简便、高效的方法.     

DpenPhos/Rh（Ⅰ） Catalyzed Asymmetric Hydrogenation of Dehydro- β -Amino Acid Esters

本文研究了一类结构可调手性单齿亚磷酰胺配体DpenPhos在Rh（I）催化的E和Z型β-脱氢氨基酸酯的不对称催化氢化反应中的应用.经过系统的反应条件和配体结构优化,发现N原子上含有H的亚磷酰胺配体与Rh（I）形成的催化剂通常比N原子上不含H的配体表现出更高的反应活性.在E型β-脱氢氨基酸酯的不对称氢化反应中,催化剂（R,R）-3k/Rh（I）表现突出,可以实现底物的常压催化氢化,取得了92%～96%的对映选择性,催化剂用量可降低至0.2 mol%;对于Z型β-脱氢氨基酸酯的不对称氢化反应,则（R,R）-3l/Rh（I）为最优催化剂,可以获得92%～98%ee值的氢化产物,特别是对于β-芳基取代衍生物的氢化反应,相应氢化产物的ee值可以达到96%～98%.该类催化剂为天然或非天然光学活性β氨基酸的合成提供了一个简便、高效的方法.     

手性醛与金属Pd联合催化氨基酸酯不对称α-烯丙基化反应

<正>J. Am. Chem. Soc. 2019, 141, 5159-5163手性醛催化在胺化学中逐渐成为一种强有力的不对称催化合成策略,化学家们利用该策略已经成功实现了转胺化、氢胺化以及氨基酸酯不对称α-官能化反应.在这些化学转化当中,手性醛催化氨基酸酯的不对称α-官能化反应在非天然手性氨基酸的合成中具有重要的应用价值.然而,已有的报道均是使用高活性的亲电试剂,如3-吲哚甲基     

CBS法合成光学活性二茂铁基醇

以非天然氨基酸合成的手性β-氨基醇(4a～4c)为催化剂，用于不对称硼烷还原反应来合成光学活性的二茂铁基醇(1a～1e)，对映体过量值高达96%。     

基于化学和对映选择性转移氢化的β,γ-炔基α-氨基酸酯的催化不对称合成研究（英文）

报道了一个通过β,γ-炔基α-亚胺酸酯的化学和对映选择性转移氢化反应来合成光学纯β,γ-炔基α-氨基酸酯的方法.该不对称还原反应所展示出的优秀的化学选择性是由手性磷酸作为催化剂以及苯并噻唑啉作为氢负供体实现的.反应展示出了良好的官能团兼容性,高对映选择性地合成了一系列光学活性的非天然氨基酸酯化合物.     

不对称加氢催化剂[Ru(BINAP)(OAc)2]的合成及其固载化研究

对文献报道的实验反应条件进行优化改进后,合成了不对称加氢催化剂[Ru((S)-BINAP)(OAc)2]和[Ru((R)-BINAP)(OAc)2]。将合成的催化剂应用于惕各酸的不对称催化氢化,(S)-2-甲基丁酸得率为88%,立体选择性可达85%e.e.。为了提高催化剂的利用率,将催化剂[Ru(BINAP)(OAc)2]负载在新型介孔分子筛SBA-15上,用于惕各酸的不对称催化氢化,循环应用3次后,(S)-2-甲基丁酸得率仍可达到59%,立体选择性达57%e.e.。     

氨基酸的不对称化学合成

氨基酸是具有重要生理活性的物质。用一般化学反应合成的α-氨基酸为外消旋体。使用不对称反应能有效地合成某一对映体过量的氨基酸。本文就近年来氨基酸不对称化学合成的一些新进展作一概述。     

Structural versatility of 5-methyltetrazolato complexes of (eta5-pentamethylcyclopentadienyl)iridium(III) incorporating 2,2'-bipyridine, N,N-dimethyldithiocarbamate, or 2-pyridinethiolate ligands

Several new mono- and dinuclear eta (5)-pentamethylcyclopentadienyl (Cp*) iridium(III) complexes bearing 5-methyltetrazolate (MeCN 4 (-)) have been synthesized and their molecular and crystal structures have been determined. For complexes incorporating 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen), both mononuclear kappa N (2)-coordinated and dinuclear mu-kappa N (1):kappa N (3)-bridging MeCN 4 complexes were obtained: [Cp*Ir(bpy or phen)(MeCN 4-kappa N (2))]PF 6 ( 1 or 3) and [{Cp*Ir(bpy or phen)} 2(mu-MeCN 4-kappa N (1):kappa N (3))](PF 6) 3 ( 2 or 4), respectively. It was confirmed by X-ray analysis that the dinuclear complex in 2 has a characteristic structure with a pyramidal pocket constructed from a mu-kappa N (1):kappa N (3)-bridging MeCN 4 (-) and two bpy ligands. In the case of analogous complexes with N, N-dimethyldithiocarbamate (Me 2dtc (-)), yellow platelet crystals of mononuclear kappa N (1)-coordinated complex, [Cp*Ir(Me 2dtc)(MeCN 4-kappa N (1))].HN 4CMe ( 5.HN 4CMe), and yellow prismatic crystals of dinuclear mu-kappa N (1):kappa N (4)-bridging one, [{Cp*Ir(Me 2dtc)} 2(mu-MeCN 4-kappa N (1):kappa N (4))]PF 6 ( 6), were deposited. The kappa N (1)- and kappa N (1):kappa N (4)-bonding modes of MeCN 4 (-) in these complexes presumably arise from the compactness of the Me 2dtc (-) coligand. 6 is the first example in which tetrazolates act as a mu-kappa N (1):kappa N (4)-bridging ligand. Furthermore, the molecular and crystal structures of dinuclear complexes having mu-kappa (2) S, N:kappa S-bridging 2-pyridinethiolate (2-Spy (-)) or 8-quinolinethiolate (8-Sqn (-)) ligands have been determined: [(Cp*Ir) 2(mu-2-Spy or 8-Sqn-kappa (2) S, N:kappa S) 2] ( 7 or 8). These thiolato-bridging complexes were stable toward the addition of 5-methyltetrazole (HN 4CMe), owing to the characteristic intramolecular stacking interaction between the pyridine or the quinoline rings. The 2-Spy complex of 7, however, reacted with an excess amount of Na(N 4CMe), resulting in cleavage of the IrN(py) bond and coordination of MeCN 4 (-) in the mu-kappa N (2):kappa N (3)-bridging mode: [(Cp*Ir) 2(mu-2-Spy-kappa S:kappa S) 2(mu-MeCN 4-kappa N (2):kappa N (3))]PF 6 ( 9). This bridging mode of MeCN 4 (-) was also observed in the triply bridging MeCN 4 complex: [(Cp*Ir) 2(mu-MeCN 4-kappa N (2):kappa N (3)) 3]PF 6 ( 10). In these various MeCN 4 complexes, the structural parameters of the MeCN 4 moiety were not perturbed by the difference in the bonding modes.     

Rapid determination of 95 pesticides in soybean oil using liquid-liquid extraction followed by centrifugation, freezing and dispersive solid phase extraction as cleanup steps and gas chromatography with mass spectrometric detection

A multi-residue method using liquid-liquid extraction (LLE) followed by centrifugation, freezing and dispersive solid phase extraction (dispersive SPE) as clean up steps and gas chromatography with mass spectrometric detection has been developed for the determination of trace levels of 95 pesticides in soybean oil. LLE has been optimized to extract these pesticide residues from soybean oil by studying the effect of different partitions between (i) acetonitrile (MeCN) saturated with petroleum ether and a soybean oil solution dissolved in petroleum ether saturated with MeCN, (ii) partition between MeCN and a soybean oil solution dissolved in petroleum ether saturated with MeCN, (iii) partition between MeCN and a soybean oil solution dissolved in petroleum ether, (iv) partition between MeCN saturated with n-hexane and a soybean oil solution dissolved in n-hexane saturated with MeCN, (v) partition between MeCN and a soybean oil solution, (vi) partition between MeCN and a soybean oil solution dissolved in n-hexane and (vii) partition between MeCN and a soybean oil solution dissolved in mixture of acetone and n-hexane (3:2) to the highest recovery yield of pesticides and the lowest co-extract fat residue in the final extract. Experiments were carried out in order to study the efficiency of using centrifugation and freezing steps as well as the used of primary secondary amine (PSA), florisil, graphite carbon black (GCB) and C18 for dispersive SPE on clean up stages to minimize the co-extract fat. The recoveries obtained ranged from 80 to 114% and the relative standard deviation (RSDs) from 2 to 14% for spiking levels of 0.040, 0.080 and 0.160 mg kg^− 1. The limits of quantification (LOQs) of almost all compounds were below the maximum residue limits (MRLs) established by the Korean legislations for soybean oil.     

Solvent-driven multiply configurable on/off fluorescent indicator of the pH window: a diethylenetriamine bearing two end pyrene fragments

Fluorescence behaviors of a simple-structured molecule (L), a diethylenetriamine bearing two end pyrene fragments, have been investigated in water. Effects of adding a less-polar organic solvent (acetonitrile: MeCN) on the emission behaviors have been studied by means of steady-state and time-resolved fluorescence measurements. L dissolved in water shows dual-mode fluorescence consisting of monomer and excimer emissions. The monomer emission shows an "on-off" intensity profile against the pH window (pH 2-12), whereas the excimer emission shows an "off-on" profile. Upon MeCN addition, the monomer emission maintains the "on-off" profile. In contrast, the "off-on" profile of the excimer emission is drastically changed: L shows two more types of profiles, "off-on-off-on" and "off-on-off", along with the MeCN concentration increase, thus behaving as a multiply configurable fluorescent indicator of the pH window. The MeCN-driven excimer emission switching of L is triggered by (i) the decrease in stability of the intramolecular ground-state dimer (GSD) formed between the end pyrene fragments, which suppresses the direct photoexcitation of GSD (suppression of the "static" excimer formation), leading to a decrease in the excimer emission intensity at basic pH; and (ii) the decrease in polarity of solution, which allows formation of a "dynamic" excimer via a monomer-to-excimer transition, resulting in an enhancement of the excimer emission intensity at acidic-neutral pH.     

IrII(ethene): metal or carbon radical?

One-electron oxidation of [(Me(n)tpa)Ir(I)(ethene)]+ complexes (Me(3)tpa = N,N,N-tri(6-methyl-2-pyridylmethyl)amine; Me(2)tpa = N-(2-pyridylmethyl)-N,N,-di[(6-methyl-2-pyridyl)methyl]-amine) results in relatively stable, five-coordinate Ir(II)-olefin species [(Me(n)tpa)Ir(II)(ethene)](2+) (1(2+): n = 3; 2(2+): n = 2). These contain a "vacant site" at iridium and a "non-innocent" ethene fragment, allowing radical type addition reactions at both the metal and the ethene ligand. The balance between metal- and ligand-centered radical behavior is influenced by the donor capacity of the solvent. In weakly coordinating solvents, 1(2+) and 2(2+) behave as moderately reactive metallo-radicals. Radical coupling of 1(2+) with NO in acetone occurs at the metal, resulting in dissociation of ethene and formation of the stable nitrosyl complex [(Me(3)tpa)Ir(NO)](2+) (6(2+)). In the coordinating solvent MeCN, 1(2+) generates more reactive radicals; [(Me(3)tpa)Ir(MeCN)(ethene)](2+) (9(2+)) by MeCN coordination, and [(Me(3)tpa)Ir(II)(MeCN)](2+) (10(2+)) by substitution of MeCN for ethene. Complex 10(2+) is a metallo-radical, like 1(2+) but more reactive. DFT calculations indicate that 9(2+) is intermediate between the slipped-olefin Ir(II)(CH(2)=CH(2)) and ethyl radical Ir(III)-CH(2)-CH(2). resonance structures, of which the latter prevails. The ethyl radical character of 9(2+) allows radical type addition reactions at the ethene ligand. Complex 2(2+) behaves similarly in MeCN. In the absence of further reagents, 1(2+) and 2(2+) convert to the ethylene bridged species [(Me(n)tpa)(MeCN)Ir(III)(mu(2)-C(2)H(4))Ir(III)(MeCN)(Me(3)tpa)](4+) (n = 3: 3(4+); n = 2: 4(4+)) in MeCN. In the presence of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxo), formation of 3(4+) from 1(2+) in MeCN is completely suppressed and only [(Me(3)tpa)Ir(III)(TEMPO(-))(MeCN)](2+) (7(2+)) is formed. This is thought to proceed via radical coupling of TEMPO at the metal center of 10(2+). In the presence of water, hydrolysis of the coordinated acetonitrile fragment of 7(2+) results in the acetamido complex [(Me(3)tpa)Ir(III)(NHC(O)CH(3)))(TEMPOH)](2+) (8(2+)).     

The 2-norbornyl cation via the fragmentations of exo- and endo-2-norbornyloxychlorocarbenes: distinction without much difference

exo- and endo-2-norbornyloxychlorocarbenes (7) were generated photochemically from the corresponding diazirines (6). Both carbenes fragmented to [2-norbornyl cation (carbon monoxide) chloride] ion pairs in MeCN or 1,2-dichloroethane solutions. Products included exo-norbornyl chloride (8), endo-norbornyl chloride (9), norbornene (10), and nortricyclene (11). Fragmentation activation energies were very low (< approximately 4 kcal/mol) and, as a result, the (laser flash photolytic) rate constants for fragmentation were essentially identical for exo-7 and endo-7 ( approximately 5 x 10(5) s(-1) in MeCN). Due to chloride return within the ion pairs, product distributions from exo- and endo-7 differed, with more endo-chloride formed from the endo-carbene: the 8/9 product ratio in MeCN was approximately 41 from exo-7, but only 4.6 from endo-7. Norbornene, formed by proton transfer to Cl(-) within the ion pairs, was a major product in both cases (44% from exo-7 and 62% from endo-7). In MeOH/MeCN, up to 28% of exo-2-norbornyl methyl ether formed at the expense of some of the norbornene, but even in 100% MeOH, the norbornyl chloride products of ion pair return still accounted for 46% and 31% of the exo-7 and endo-7 product mixtures (accompanied by 26-32% of norbornene). Electronic structure calculations on the ground states and fragmentation transition states of exo-7 and endo-7 are presented.     

Experimental and theoretical investigations on the catalytic hydrosilylation of carbon dioxide with ruthenium nitrile complexes

Ruthenium complexes, mer-[RuX(3)(MeCN)(3)] and cis/trans-[RuX(2)(MeCN)(4)] with X=Br, Cl, were investigated as precatalysts in homogeneously catalyzed hydrosilylation of CO(2). The oxidation state of ruthenium and nature of the halide in the precatalysts were found to influence the catalytic activity in the conversion of Me(2)PhSiH to the formoxysilane Me(2)PhSiOCHO, with Ru(III) having chloride ligands being most active. Monitoring the reactions by in-situ IR spectroscopy in MeCN as the solvent indicates an interaction of the precatalyst with the silane prior to activation of CO(2). In the absence of CO(2), hydrosilylation of the MeCN solvent occurs. Catalytic activity in CO(2) hydrosilylation is enhanced by Me(2)PhSiCl, generated during reduction of Ru(III) in mer-[RuX(3)(MeCN)(3)] to Ru(II) or, when added as promoter to Ru(II) precatalysts. The reaction mechanism for the catalytic cycle has been calculated by DFT methods for the reaction of Me(3)SiH. The key steps are: Transfer of the Me(3)Si moiety to a coordinated halide ligand, resulting in an L(n)RuH(XSiMe(3)) intermediate --> CO(2) coordination --> Me(3)Si transfer to CO(2) --> reductive elimination of formoxysilane product. This reaction sequence is more favorable energetically for chloride complexes than for the analogous bromide complexes, which accounts for their differences in catalytic activity. Calculations also explain the rate increase observed experimentally in the presence of Me(2)PhSiCl. A parallel reaction pathway leads to (Me(3)Si)(2)O as a minor byproduct which arises from the condensation of two initially formed Me(3)SiOH molecules.     

Partial spin crossover behaviour in a dinuclear iron(II) triple helicate

Reported herein are the synthesis, structural, magnetic and M?ssbauer spectroscopic characterisation of a dinuclear Fe(II) triple helicate complex [Fe(2)(L)(3)](ClO(4))(4).xH(2)O (x = 1-4), 1(H(2)O), where L is a bis-bidentate imidazolimine ligand. Low temperature structural analysis (150 K) and M?ssbauer spectroscopy (4.5 K) are consistent with one of the Fe(II) centres within the helicate being in the low spin (LS) state with the other being in the high-spin (HS) state resulting in a [LS:HS] species. However, M?ssbauer spectroscopy (295 K) and variable temperature magnetic susceptibility measurements (4.5-300 K) reveal that 1(H(2)O) undergoes a reversible single step spin crossover at one Fe(II) centre at higher temperatures resulting in a [HS:HS] species. Indeed, the T(1/2)(SCO) values at this Fe(II) centre also vary as the degree of hydration, x, within 1(H(2)O) changes from 1 to 4 and are centred between ca. 210 K-265 K, respectively. The dehydration/hydration cycle is reversible and the fully hydrated phase of 1(H(2)O) may be recovered on exposure to water vapour. This magnetic behaviour is in contrast to that observed in the related compound [Fe(2)(L)(3)](ClO(4))(4)·2MeCN, 1(MeCN), whereby fully reversible SCO was observed at each Fe(II) centre to give [LS:LS] species at low temperature and [HS:HS] species at higher temperatures. Reasons for this differing behaviour between 1(H(2)O) and 1(MeCN) are discussed.     

Single-molecule magnets: a Mn25 complex with a record S = 51/2 spin for a molecular species

The reaction of MnCl2.4H2O (3 equiv), pyridine-2,6-dimethanol (pdmH2) (10 equiv), and NaN3 (10 equiv) in MeOH/MeCN (1:2 v/v) with NMe4OH (1 equiv) gave [Mn25O18(OH)2(N3)12(pdm)6(pdmH)6](Cl)2.12MeCN (1.12MeCN) in approximately 30% yield. The cation of complex 1 comprises five Mnx layers of three types in an ABCBA arrangement. Fitting of variable-temperature and -field magnetization data establishes that 1 has an S = 51/2 ground state, the largest value for a molecular species. The complex also displays hysteresis loops below 0.6 K in magnetization vs applied field sweeps, establishing it as the largest spin single-molecule magnet to date.     

Asymmetric 1,3-dipolar cycloaddition of N-metalated azomethine ylides to methyl (S)-2-(p-tolylsulfinyl)acrylate. Synthesis of optically pure 2,4,5-trisubstituted 2,5-dihydro-1H-pyrroles

The first 1,3-dipolar reaction of azomethine ylides with optically pure vinyl sulfoxide are reported. The presence of the sulfinyl group increase the reactivity of the acrylate moiety as a dipolarophile, and the reactions evolve with complete regio- and endo-selectivities. Nevertheless, mixtures of the two diastereoisomers 4 and 5 (75-88% de) resulting from the anti dipole/s-cis dipolarophile and syn dipole/s-trans dipolarophile approaches, respectively, are obtained. The stereoselectivity can be controlled by using THF or MeCN as solvents or by changing the reaction temperature in MeCN. After separation of the cycloadducts, optically pure 2,5-dihydro-1H-pyrroles are easily obtained by pyrolytic desulfinylation.     

Incorporation of substitutionally labile [V(III)(CN)6]3- into prussian blue type magnetic materials

A Prussian blue (PB) type material containing hexacyanovanadate(III), Mn(II)1.5[V(III)(CN)6].(0.30)MeCN (1), was formed from the reaction of [V(III)(CN)6](3-) with [Mn(NCMe)6](2+) in MeCN. This new material exhibits ferrimagnetic spin- or cluster-glass behavior below a Tc of 12K with observed magnetic hysteresis at 2 K (Hcr = 65 Oe and Mrem = 730 emu.Oe/mol). Reactions of [V(III)(CN)6](3-) with [M(II)(NCMe)6](2+) (M = Fe, Co, Ni) in MeCN lead to either partial (M = Co) or complete (M = Fe, Ni) linkage isomerization, resulting in compounds of Fe(II)(0.5)V(III)[Fe(II)(CN)6].(0.85)MeCN (2), (NEt4)(0.10)Co(II)(1.5- a)V(II)a[Co(III)(CN)6]a [V(III)(CN)6](1-a)(BF4)(0.10).(0.35)MeCN (3), and (NEt4)(0.20)V(III)[Ni(II)(CN)4](1.6).(0.10)MeCN (4) compositions. Compounds 2-4 do not magnetically order as a consequence of diamagnetic cyanometalate anions being present, i.e., [Fe(II)(CN)6](4-), [Co(III)(CN)6](3-), and [Ni(II)(CN)4](2-). Incorporation of [V(III)(CN)6](3-) into PB-type materials is synthetically challenging because of the lability of the cyanovanadate(III) anion.