Chiral copper-bipyridine complexes: Synthesis, characterization and mechanistic studies on asymmetric cyclopropanation

Chiral bipyridine ligands of different steric properties when reacted with CuCl₂ formed orange, yellow or green solids of new copper(II) complexes, [Cu(L)Cl₂] (L = L2-6), in good yield. Together with [Cu(L1)Cl₂], these complexes were characterized in solution by UV-Vis spectroscopy and cyclic voltammetry. The complexes give d-d transitions between 860 and 970 nm, and exhibit one quasi-reversible Cu(II)/Cu(I) couple between +0.405 V and +0.516 V versus NHE. Two of the copper(II) complexes, [Cu(L5)Cl₂] and [Cu(L6)Cl₂], and a copper(I) complex of L1, [Cu(L1)Cl], were characterized by X-ray crystallography. The triflate derivatives of both the Cu(I) and Cu(II) complexes are active catalysts towards the cyclopropanation of ethyl diazoacetate with styrene. The asymmetric induction suffers when the size difference between the alkyl and alkoxyl groups was minimized. The mechanism of the cyclopropanation was studied with kinetic and competition experiments. The rate is first order in catalyst and ethyl diazoacetate, inverse order with styrene and is strongly affected by the counterion.     

Enantioselective synthesis of oseltamivir phosphate

The key steps in the enantioselective synthesis of Tamiflu include an asymmetric Diels-Alder reaction, Mitsunobu inversion using Fukuyama modified Weinreb reagent, carbamate directed epoxidation. Epoxide opening with trimethylsilyl azide furnished a 3:1 mixture of regioisomers that converged to afford the same aziridine. Attempted preparation of the unsaturated ester regioselectively using 2-iodoxybenzoic acid (IBX) following Nicolaou’s protocol failed. The unsaturated ester was prepared by phenylselenylation followed by selenoxide elimination.     

The first example for the asymmetric synthesis of allenes by the Doering-LaFlamme allene synthesis with enantiopure cyclopropylmagnesium carbenoids

The reaction of lithium α-sulfinyl carbanion of enantiopure dichloromethyl p-tolyl sulfoxide with α,β-unsaturated carbonyl compounds gave optically active 1-chlorocyclopropyl p-tolyl sulfoxides having a carbonyl group with high asymmetric induction from the sulfur chiral center. Reduction of the carbonyl group followed by treatment with Grignard reagent, the 1-chlorocyclopropyl p-tolyl sulfoxides resulted in the formation of enantiopure allenic alcohols via the Doering-LaFlamme-type rearrangement of enantiopure cyclopropylmagnesium carbenoid intermediates. This is the first example for the asymmetric synthesis of allenes by the Doering-LaFlamme allene synthesis.     

Total synthesis of the antiinflammatory and proresolving protectin D1

Stereoselective total synthesis of protectin D1 was completed through construction of the Z,E,E-triene structure by using the Suzuki coupling between the vinyl borane (C13-C22) and the vinyl iodide (C1-C12). The Z-enyne, the acetylene precursor of the vinyl borane was synthesized from optically active γ-TMS allylic alcohol in a straightforward way. On the other hand, the vinyl iodide was prepared by using Wittig reaction between the C8-C12 aldehyde possessing the requisite iodo-olefin moiety and the C1-C7 phosphonium iodide.     

Lead(IV) acetate oxidative ring-opening of 2,3-epoxy primary alcohols: a new entry to optically active α-hydroxy carbonyl compounds

The treatment of 2,3-epoxy primary alcohols with lead(IV) acetate (LTA) leads to α-acetoxy aldehydes or α-acetoxy ketones, through the nucleophilic ring-opening of an intermediate oxonium and the subsequent carbon-carbon bond cleavage. This reaction represents a new route to optically active α-hydroxy carbonyl compounds.     

双通道离子色谱法同步检测DOPO中的无机离子

以氯仿溶解9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO),离心取清液,自动进样器-双通道离子色谱法同步检测DOPO中的无机阴阳离子,采用自动进样器与双通道同步进行,大大缩短了分析时间,离子保留时间的相对标准偏差RSD(n=6)在0.07%～0.18%,峰面积的RSD(n=6)在0.43%～0.88%,重现性好。3种离子的平均回收率在94.87%～98.30%,结果令人满意。     

Synthesis and Crystal Structure of （R）-4-Hydroxymethyl-2-thioxo Thiazolidine and Its Asymmetric Catalysis

(R)-4-Hydroxymethyl-2-thioxo thiazolidine as a new chiral catalyst in the asymmetric addition of diethyl-zinc to benzaldehyde was synthesized from (R)-4-hydroxymethyl-2-thioxo thiazolidine carboxylic acid and its crystal structure was determined by X-ray diffraction method. The compound was crystallized in the orthorhombic system, space group P212121 with unit cell dimensions a=0.67253(12) nm; b=0.89164(17) rim; c=1.06146(19) nm, volume 0.6365(2) nm3; Z=4, calculated denisity 1.557 Mg/m3; absorption coefficient 0.733 mm-1; F(000)=312. The X-ray crystal structure analysis reveals that the compound has a thione group.     

Nanoporous asymmetric polyaniline films for filtration of organic solvents

A new family of functional materials is reported for organic solvent nanofiltration, with excellent chemical stability and high retention of solute molecules. Integrally skinned asymmetric polyaniline (PANI) membranes were fabricated from concentrated solutions of doped PANI by phase inversion. Doped PANI solutions were prepared by adding organic acids directly to PANI dissolved in a mixture of NMP and 4-methyl piperidine before casting. Among the organic acids investigated, maleic acid, phthalic acid, sulfosalicylic acid and camphorsulfonic acid were able to dope PANI without causing gelation. These acids acted as soft templates, creating nanoporosity in the thin skin layer of the asymmetric PANI film. Their removal by alkaline extraction created membranes through which small solvent molecules can pass. After extracting the organic acids, the membranes were thermally crosslinked which conferred excellent solvent stability. These membranes had a molecular weight cut-off (MWCO) in the range of 150–250 g mol⁻¹ in methanol, making them the tightest OSN membranes reported to date. It was found that an increase in crosslinking temperature or time led to a decrease in solvent flux. PANI membranes were found to be resistant to a variety of organic solvents such as ethyl acetate, acetonitrile and acetone. These remarkable membranes have the potential to be used in OSN operations at high temperatures (up to 150 °C), and gave increasing fluxes with increasing temperature while maintaining a high solute rejection.     

烯烃的有机催化不对称环氧化反应

介绍了用手性酮,手性亚胺盐为催化剂以及手性胺为催化剂前体的新型有机催化不对称环氧化反应。