Hydrogen‐Bonding‐Driven Enantioselective Resolution against the Kazlauskas Rule To Afford γ‐Amino Alcohols by Candida rugosa Lipase

Most lipases resolve secondary alcohols in accordance with the “Kazlauskas rule” to give the R enantiomers. In a similar manner to other lipases, Candida rugosa lipase (CRL) exhibits R enantioselectivity towards heptan‐2‐ol, although the enantiomeric ratio (E) is low (E=1.6). However, unexpected enantioselectivity (i.e., S enantioselectivity, E=58) of CRL towards 4‐(tert‐butoxycarbonylamino)butan‐2‐ol, which has a similar chain length to heptan‐2‐ol, has been observed. To develop a deeper understanding of the molecular basis for this unusual enantioselectivity, we have conducted a series of molecular modeling and substrate engineering experiments. The results of these computational and experimental analyses indicated that a hydrogen bond between the Ser450 residue and the nitrogen atom of the carbamate group is critical to stabilize the transition state of the S enantiomer.     

Palladium‐Catalyzed Three‐Component Reaction of 3‐(Tri‐n‐ butylstannyl)allyl Acetates,Aldehydes, and Triorganoboranes: An Alternative to the Carbonyl Allylation Using α,γ‐Substituted Allylic Tin Reagents

A three‐component reaction of 3‐(tri‐n‐butylstannyl)allyl acetates, aldehydes, and triorganoboranes in the presence of a palladium‐Xantphos catalyst system predominately gave (E)‐anti‐homoallylic alcohols with high diastereoselectivity and good to high levels of alkene stereocontrol. An efficient chirality transfer was observed when an enantioenriched substrate was employed. The reaction was initiated by the formation of an allylic gem‐palladium/stannyl intermediate, which subsequently underwent allylation of the aldehyde by an allyltributyltin followed by a coupling reaction of the in‐situ‐generated (E)‐vinylpalladium acetate with the triorganoborane.

     

Improved Second Generation Iron Pincer Complexes for Effective Ester Hydrogenation

Hydrogenation of esters to alcohols with a well‐defined iron ^iPr2PNP pincer complex has been recently reported by us and other groups. We now introduce a novel and sterically less hindered ^Et2PNP congener that provides superior catalytic activity in the hydrogenation of various carboxylic acid esters and lactones compared to the known complex. Successful hydrogenation proceeds under relatively mild conditions (60 °C) with lower catalyst loadings.

     

Production of pharmaceuticals: Amines from alcohols in a continuous flow fixed bed catalytic reactor

This paper reports the use of an immobilised ruthenium complex in a continuous flow process for the N-alkylation of morpholine with benzyl alcohol. The ruthenium-based catalyst was supported on a phosphine bound polymer. Screening experiments were first performed in a batch reactor, with a 16 vol% mixture of morpholine and benzyl alcohol (stoichiometric molar ratio of 1:1) in toluene as the solvent. Operating at 110 °C for 24 h, it was shown that high conversions (>99%) into the desired tertiary amine could be achieved. This reaction was then shown to be viable in a continuous flow reactor, where the catalytic polymer beads were retained in the bed. Operating at 150 °C and using p-xylene as a solvent, the conversion into the desired tertiary amine was shown to be as high as 98%. This approach is clearly very promising, as it provides a greener and more atom efficient route for the production of secondary and tertiary amines in the pharmaceutical industry.     

Photo-electro catalytic oxidation of aromatic alcohols on visible light-absorbing nitrogen-doped TiO2

Visible light illumination of nitrogen-doped TiO₂ brings about the selective oxidation of benzyl and cinnamyl alcohol to the corresponding aldehydes. The photocatalyst was prepared by a sol-gel method and characterised mainly by XRD, UV-vis diffuse reflectance and Raman spectroscopy. The conditions limiting the observation of visible light photoactivity are the use of dry nitriles as nonaqueous solvents and aromatic alcohols as the substrates. No visible light oxidation takes place in an aqueous medium. The efficiency of benzyl and cinnamyl alcohol photo-oxidation in nitrile solvents follows the order: CH₃CN > CH₃CH₂CN > CH₃(CH₂)₂CN. Conversely, since alcohol photo-oxidation occurs with 100% selectivity on electrodes in O₂ saturated solutions at potentials close to E_fb or under open-circuit conditions, suspensions of the photocatalyst can be advantageously employed. The process involves a relatively weak adsorption of the alcohol substrates which, however, do not readily capture the photogenerated holes. On the basis of the electrochemical and photoluminescence data, it appears that the solvent (e.g. acetonitrile), in addition to O₂ has an active role in the reaction mechanism.     

The First Example of Saccharin‐Lithium Bromide Catalysis: Direct Synthesis of N‐Tosylimines from Alcohols

The first procedure to access N‐tosylimines directly from alcohols under mild and neutral conditions is reported. The protocol involves saccharin‐lithium bromide‐catalyzed oxidation of alcohols to aldehydes/ketones with chloramine‐T followed by their condensation with the in situ generated oxidation by‐product p‐toluenesulfonamide in the same reaction vessel to afford N‐tosylimines in 40–90% overall yields. The present work opens up a new and efficient synthetic route to N‐tosyimines directly from alcohols in a one‐pot procedure.     

乙醇缩合制高碳醇(C6+醇)多相催化剂研究进展

以乙醇为原料制备其他高附加值化工产品近期得到了广泛关注,特别是乙醇基于Guerbet反应缩合制备高碳醇(C₆₊)的过程更成为这一领域的研究热点。本文着重报道了近年来乙醇转化为高碳醇过程的几种典型的多相催化剂,包括羟基磷灰石(HAP)、类水滑石(LDHs)以及各种负载型金属催化剂的研究开发现状,分析比较了各类催化剂的优势与不足,结合反应机理针对催化剂对高碳醇选择性不高的原因进行了讨论,对理想催化剂的设计和改进进行了展望,指出应该通过促进Guerbet反应中的羟醛缩合过程增加高碳醇的选择性。金属负载型催化剂对该反应控制步骤的加速作用显著,而金属位点和载体表面酸碱活性位点的精细调控以及特定催化剂形貌结构的控制合成则是该领域未来的研究重点。     

ONE HUNDRED YEARS OF YEAST RESEARCH AND DEVELOPMENT IN THE BREWING INDUSTRY

The effect that yeast research and development on yeasts has had on the brewing industry is traced from the time of Pasteur to the present time.     

FFAP毛细管柱直接进样测定白酒中微量成分

以叔戊醇、乙酸正戊酯、2-乙基正丁酸的混合液为内标，在BP21型FFAP毛细管柱上直接进样测定白酒中的醇酯酸等香味物质。此法简单、快速、准确。且分析数据应用于指导监测白酒生产，提供了更多有效信息。     

PbTiO3催化剂上CO水合制低碳醇过程研究

在固定床微反反应器上，对CO水合制低碳醇反应催化剂进行评价，通过对金属氧化物活性组份的筛选，发现Pb—TiO3催化剂具有较佳的催化反应性能。考察了碱金属碳酸盐类助剂对反应活性的影响，实验结果表明，碱金属碳酸盐随溶解度的增加对反应的促进作用明显增加，产物中醇的总收率顺序为K2CO3＞Na2CO3＞Li2CO3；溶剂的作用与其碱性有密切关系，强碱性的有机多胺能够有效促进该反应，相对于非极性溶剂的醇收率2．0mg/g/h，在碱性溶剂中相同催化剂的活性最高可达到23．1mg/g/h。TPR结果表明，与PbO相比，PbTiO3在反应条件下不易被还原。另外，对反应机理也进行了初步探讨。