Synthesis of 2H-pyrrolo[3,4-C]quinoline via an Aldol/Van Leusen/Staudinger/aza-Wittig sequence

An aldol/van Leusen/Staudinger/aza-Wittig reaction for the preparation of the derivatives of 2H-pyrrolo[3,4-c]quinolines from 2-azidobenzaldehyde, acetyl compounds, and tosylmethyl isocyanide was developed. The process involves an aldol condensation of 2-azidobenzaldehyde with acetyl compound in base, a van Leusen reaction to form the key pyrrole intermediates, and then a Staudinger and intramolecular aza-Wittig reaction occurred with the addition of triphenylphosphine to complete the formation of pyrrolo[3,4-c]quinoline ring in high yields.     

Unexpected synthesis of indolo[1,2-c]quinazolines by a sequential Ugi 4CC-Staudinger-aza-Wittig-nucleophilic addition reaction

A new sequential Ugi-Staudinger-aza-Wittig-nucleophilic addition reaction was developed to construct indolo[1,2-c]quinazoline derivatives, starting from the easily accessible 2-azidobenzaldehyde, carboxylic acid, 2-acylaniline and isocyanide. It is noteworthy that this is the first report of the cyclization of the Ugi adduct to give a dihydroindole ring system with two quaternary carbon centers, via the nucleophilic addition reaction of the methine group to the carbonyl group.     

New efficient synthesis of 1H-imidazo-[4,5-c]quinolines by a sequential Van Leusen/Staudinger/aza-Wittig/carbodiimide-mediated cyclization

A new efficient synthesis of multisubstituted 1H-imidazo-[4,5-c]quinoline derivatives via sequential van Leusen/Staudinger/aza-Wittig/carbodiimide-mediated cyclization was developed. Azides 4, obtained from Van Leusen reaction of 2-azidobenzaldehyde 1, amine 2 and TosMIC (tosylmethyl isocyanide) 3, reacted with triphenyl phosphine to produce iminophosphorane 5. A tandem aza-Wittig reaction of iminophosphorane 5 with isocyanate generated 1H-imidazo-[4,5-c]quinoline 7 through carbodiimide intermediate 6 in moderate to good yield.     

A simple and one-pot synthesis of 2,3,4,5-tetrasubstituted 4,5-dihydro-3H-1,4-benzodiazepines

2,3,4,5-Tetrasubstituted 4,5-dihydro-3H-1,4-benzodiazepines were synthesized in one-pot by a new sequential Ugi 4CC/Staudinger/aza-Wittig reaction, starting from easily accessible o-azidobenzaldehyde, α-amino ketone hydrochloride, isocyanide and carboxylic acid.     

Synthesis of (arylselanyl)- and (arylsulfenyl)-alkyl-1,2,3-triazolo-1,3,6-triazonines via a copper-catalyzed multicomponent reaction

An efficient copper-catalyzed multicomponent reaction was developed for the synthesis of (arylselanyl)- or (arylsulfenyl)-alkyl-1,2,3-triazolo-1,3,6-triazonines. The products were obtained in moderate to excellent yields via the reaction of o-phenylenediamine, 2-azidobenzaldehyde and different arylchalcogenyl alkynes using catalytic copper iodide in 1,4-dioxane at 100?°C. The reactions tolerated a range of substituents on the arylchalcogenyl alkynes and proved to be an efficient methodology for the combinatorial synthesis of new selenium or sulfur-containing triazonine derivatives.     

New efficient synthesis of pyrimido[1,6-c]quinazolin-4-ones by a Biginelli 3CC/Staudinger/aza-Wittig sequence

Dihydropyrimidinone azides 1, obtained from trimethylsilyl chloride-catalyzed Biginelli reaction of 2-azidobenzaldehyde, ethyl acetoacetate, and urea (or thiourea) at room temperature, reacted with triphenylphosphine to give iminophosphorane 2. A tandem aza-Wittig reaction of iminophosphorane 2 with isocyanate, acyl chloride or CS₂ in the presence of K₂CO₃ or NEt₃ generated pyrimido[1,6-c]quinazolin-4-ones 4, 6 or 8 in moderate to good yield.     

New efficient synthesis of 4-aminocarbonyl substituted 4H-3,1-benzoxazines by a Passerini 3CC/Staudinger/aza-Wittig sequence

α-Acyloxy-carboxamide azides 1, obtained from Passerini reaction of easily accessible o-azidobenzaldehyde with isocyanides and carboxylic acids, reacted with triphenylphosphine to give various 4-aminocarbonyl substituted 4H-1,3-benzoxazines 3 in moderate to high yields via sequential Staudinger and intramolecular aza-Wittig reaction. However, α-hydroxy carboxamide azides 5 were obtained in moderate yields when pyruvic acid was used in the Passerini reaction. Further sequential reaction of azides 5 with triphenylphosphine and isocyanates produced 2-amino-4-aminocarbonyl substituted 4H-1,3-benzoxazines 8 via a tandem Staudinger/aza-Wittig/heterocumulene-mediated annulation.     

Selective 1,4-reduction of unsaturated carbonyl compounds using Co2(CO)8-H2O

α,β-Unsaturated ketones and aldehydes were selectively reduced to the corresponding saturated carbonyl compounds by Co₂(CO)₈-H₂O system. The current reducing system also offered a chemoselective reduction of less substituted unsaturated carbonyl groups.     

RhCo双金属催化剂的研究III. Rh+Co/Al2O3上表面羰基氢化物及其动态行为

利用连续流动微反研究了Rh+Co/Al2O3催化剂的CO加氢反应, 结果表明反应在220℃以上发生, 反应活性随着温度的升高和H2/CO值的增加而增加。利用TP-IR动态方法研究了Rh+Co/Al2O3上CO和H2共吸附及其动态行为。结果表明在Rh+Co/Al2O3的孪生及线式中心上, CO和H2室温共吸附时即有部分孪生及线式CO转化为相应的羰基氢化物, 随着温度的升高, 剩余的孪生和线式CO继续向相应的羰基氢化物转化。而羰基氢化物则向多羰基氢化物转化。在到达反应温度之前, 催化剂表面只存在羰基氢化物及相应的多氢羰基氢化物。在反应温度则导致产物CH4生成。与CO加氢反应和CO歧化的吸附态研究结果相关联, 作者认为Rh+Co/Al2O3上CO加氢生成CH4是经由羰基氢化物-多氢羰基氢化物途径。     

Design, synthesis, structure and properties of an α-helix cap template derived from N-[(2S)-2-chloropropionyl]-(2S)-Pro-(2R)-Ala-(2S,4S)-4-thioPro-OMe which initiates α-helical structures

A strategy based upon removing the requirement for all of the carbonyl dipoles to align at the same time in the transition state leading to the cyclisation of N-[(2S)-2-chloropropionyl]-(2S)-Pro-(2R)-Ala-(2S,4S)-4-thioPro-OMe to a Zimm-Bragg type α-helix peptide intitator template was successful. Each amide bond of the 12-membered macrocyclic template existed in the trans-rotomeric form. Derivatives of the template were prepared by extending the C-terminus and these were characterised by NMR spectroscopy and restrained simulated annealing. In deuterochloroform solution at low temperature, separate sets of NMR signals were observed for two rapidly interconverting helical conformational isomers of the thioether macrocycle which possessed an appended trialkylammonium ion. A similar time-averaged conformation was also observed in aqueous solution. At −80 °C in d₂-dichloromethane the rate of conformational exchange was slowed sufficiently to obtain resonance assignments and NOE data separately for each isomer. In the minor isomer (40%), the four carbonyl oxygen hydrogen-bond acceptors of the template are aligned in an α-helical conformation and in the major conformer the Pro² carbonyl dipole was anti-aligned with the other three dipoles. Thus, the conformers differ in the orientation of one carbonyl group. Molecular modelling calculations showed that the minor isomer was stabilised by coulombic interactions between the trialkylammonium salt and the carbonyl group dipole moments.     

担载的Co2(CO)6(PBu3)2络合物的表面化学

红外光谱表明当Co_2(CO)_6(PBu_3)_2羰基络合物担载于不同的氧化物上后, 其羰基振动频带位置的波数顺序为: 络合物/SiO_2=络合物/TiO_2>络合物/Al_2O_3>络合物/ZrO_2。当这四种担载络合物在真空中加热脱羰基时, 以ZrO_2和Al_2O_3为载体者出现相当于桥式配位羰基的振动频带, 分别至300 ℃和200 ℃时羰基完全脱去。以TiO_2和SiO_2为载体者,基本没有出现桥羰基的频带, 而且在较低的温度下羰基即可脱去。紫外漫反射光谱表明担载络合物与担载前相比其表征Co-Co键和Co—Co配位键性质的特征带仍然存在, 脱羰基后出现相当于Co~(+2)或Co_3O_4的特征谱带。程序升温分解反应发现在H_2气氛中有表面加氢反应发生。     

Ph2S2-CaH2 in N-methyl-2-pyrrolidone as an efficient protocol for chemoselective cleavage of aryl alkyl ethers

CaH₂ was been found, for the first time, as a mild reducing agent to generate thiophenolate anion from Ph₂S₂ in N-methyl-2-pyrrolidone (NMP) for deprotection of aryl alkyl ethers. Excellent chemoselctivity was observed for substrates having chloro and nitro groups without displacement of the chlorine atom and the nitro group. Selective ether cleavage took place in the presence of α,β-unsaturated carbonyl and nitro groups without reduction and conjugate addition (to the α,β-unsaturated carbonyl group).     

Synthetic scope of Ru(OH)x/Al2O3-catalyzed hydrogen-transfer reactions: an application to reduction of allylic alcohols by a sequential process of isomerization/Meerwein-Ponndorf-Verley-type reduction

Reduction of allylic alcohols can be promoted efficiently by the supported ruthenium catalyst Ru(OH)x/Al2O3. Various allylic alcohols were converted to saturated alcohols in excellent yields by using 2-propanol without any additives. This Ru(OH)x/Al2O3-catalyzed reduction of a dienol proceeds only at the allylic double bond to afford the corresponding enol, and chemoselective isomerization and reduction can be realized under similar conditions. The catalysis is truly heterogeneous and the high catalytic performance can be maintained during at least three recycles of the Ru(OH)x/Al2O3 catalyst. The transformation of allylic alcohols to saturated alcohols consists of three sequential reactions: oxidation of allylic alcohols to alpha,beta-unsaturated carbonyl compounds; reduction of alpha,beta-unsaturated carbonyl compounds to saturated carbonyl compounds; and reduction of saturated carbonyl compounds to saturated alcohols.     

Efficient hydrosilylation of carbonyl compounds by 1,1,3,3-tetramethyldisiloxane catalyzed by Au/TiO2

1,1,3,3-Tetramethyldisiloxane (TMDS) is a highly reactive reducing reagent in the Au/TiO₂-catalyzed hydrosilylation of carbonyl compounds relative to monohydrosilanes. The reduction of aldehydes or ketones with TMDS can be performed on many occasions at ambient conditions within short reaction times and at low loading levels of gold, whereas typical monohydrosilanes require excess heating and prolonged time for completion. The product yields are excellent, while almost stoichiometric amounts of carbonyl compounds and TMDS can be used. It is postulated that the enhanced reactivity of TMDS is attributed to the formation of a gold dihydride intermediate. This intermediate is also supported by the fact that double hydrosilylation of carbonyl compounds by TMDS is a negligible pathway.     

An investigation into the mechanism of conversion of fac-[Mn(CO)3{P(OMe)2Ph}2X] (X = Cl Br) into mer-cis-[MnCO2{P(OMe)2Ph}3X] in the presence of P(OMe)2Ph

The complex mer-trans-[Mn(CO)₃{P(OMe)₂Ph}₂X] (X = Cl, Br) is an intermediate in the conversion of fac-[Mn(CO)3{P(OMe)₂,Ph}₂,X] into mer- cis-[Mn(CO)₂{P(OMe)₂Ph}₃X] in the presence of P(OMe)₂Ph in benzene. No direct route between the latter two complexes could be detected kinetically. The results imply a trans carbonyl disposition as a prerequisite for higher carbonyl substitution in octahedral Mn¹ carbonyl complexes.     

A molecular orbital study of lithium ion association with bases. I. The carbonyl bases R2CO

Ab initio SCF calculations have been performed to determine the relative lithium ion affinities of the carbonyl bases R₂CO and the structures of the complexes R₂COLi⁺. The predicted order of lithium ion affinity for the bases R₂CO with respect to R is NH₂ > CH₃ > OH> H> F. Except for (OH)₂COLi⁺ which has C_a, symmetry, the complexes R₂COLi⁺ have C_2v symmetry, with the lithium ion located on the symmetry axis near the oxygen. The major structural changes in the intramolecular coordinates of the bases which occur upon lithium ion complexation include an increase in the carbonyl C---O bond length, a decrease in the length of the bond from the carbonyl carbon to the substituent atom X, and an increase in the X---C---X angle at the carbonyl carbon. The energetic, structural, and electronic properties of the complexes indicate that the interaction between the lithium ion and a carbonyl base is predominantly an ion-dipole attraction rather than a covalent interaction.     

A green and efficient deoximation using H202 catalyzed by montmorillonite-K10 supported COC12

Oximes were oxidized to the corresponding carbonyl compounds in good to high yields by environmentally friendly and green oxidant, H202 catalyzed by montmorillonite K-10 supported cobalt（Ⅱ） chloride.     

Oxidative-substitution reactions of electron-rich aromatic compounds with BF3-activated iodonium ylides

The treatment of electron-rich aromatic substrates with phenyliodonium bis(carbonyl)methylides in the presence of Et₂O·BF₃ leads to bis(carbonyl)alkylation of the aromatic nucleus.     

Combination of NH2OH·HCl and NaIO4: a new and mild oxidizing agent for selective oxidation of alcohols to carbonyl compounds

A new method for oxidation of alcohols to carbonyl compounds has been developed using NH₂OH·HCl and NaIO₄ under mild reaction conditions at room temperature. Application of the method for the synthesis of diiodo compound from α,β-unsaturated carbonyl compound is also described.     

Reformatsky type reaction by means of Bu3SnA1et2 or Bu3Pba1et2

Treatment of α-halo carbonyl compounds with title Sn-Al or Pb-Al reagents provides enolates which react with aldehydes or ketones to give β-hydroxy carbonyl compounds effectively.