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81.
Manzano R Andrés JM Álvarez R Muruzábal MD de Lera ÁR Pedrosa R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(21):5931-5938
A series of chiral thioureas derived from easily available diamines, prepared from α-amino acids, have been tested as catalysts in the enantioselective Michael additions of nitroalkanes to α,β-unsaturated ketones. The best results are obtained with the bifunctional catalyst prepared from L-valine. This thiourea promotes the reaction with high enantioselectivities and chemical yields for aryl/vinyl ketones, but the enantiomeric ratio for alkyl/vinyl derivatives is very modest. The addition of substituted nitromethanes led to the corresponding adducts with excellent enantioselectivity but very poor diastereoselectivity. Evidence for the isomerization of the addition products has been obtained from the reaction of chalcone with [D(3)]nitromethane, which shows that the final addition products epimerize under the reaction conditions. The epimerization explains the low diastereoselectivity observed in the formation of adducts with two adjacent tertiary stereocenters. Density functional studies of the transition structures corresponding to two alternative activation modes of the nitroalkanes and α,β-unsaturated ketones by the bifunctional organocatalyst have been carried out at the B3LYP/3-21G* level. The computations are consistent with a reaction model involving the Michael addition of the thiourea-activated nitronate to the ketone activated by the protonated amine of the organocatalyst. The enantioselectivities predicted by the computations are consistent with the experimental values obtained for aryl- and alkyl-substituted α,β-unsaturated ketones. 相似文献
82.
83.
Cong Duan Yongqi Yao Ling Ye Zhichuan Shi Zhigang Zhao Xuefeng Li 《Tetrahedron》2018,74(50):7179-7185
An efficient cascade aza-Michael-Michael sequence for the preparation of tetrahydroquinolines has been established. Three contiguous stereogenic centers are created with high levels of enantioselectivities (79–99% ee) and exclusive diastereoselectivities in the presence of a bifunctional squaramide. This approach is compatible with a broad range of β,γ-unsaturated α-ketoesters and 2-aminochalcones. Our protocol indicated that β-site of β,γ-unsaturated α-ketoester is an available pro-nucleophilic site. 相似文献
84.
Wen-Fei Hu Jian-Qiang Zhao Xiao-Zhen Chen Ming-Qiang Zhou Xiao-Mei Zhang Xiao-Ying Xu Wei-Cheng Yuan 《Tetrahedron》2019,75(14):2206-2214
An organocatalyzed asymmetric sulfa-Michael addition of thiocarboxylic acids to β-trifluoromethyl-α,β-unsaturated ketones with a chiral bifunctional amine-squaramide as the catalyst is presented. A wide range of chiral ketone compounds bearing a sulfur atom and a trifluoromethyl group at the stereogenic carbon center could be obtained with excellent results (up to 99% yield, 97% ee) under mild conditions. The developed catalytic system is well-tolerated to both (E)-and (Z)-β-trifluoromethylated-α,β-unsaturated ketones. 相似文献
85.
Fabio BonaLuisella De Vitis Saverio FlorioLudovico Ronzini Luigino Troisi 《Tetrahedron》2003,59(9):1381-1387
2-Chloroalkylthiazolyllithiums, prepared by deprotonating the 2-chloroalkylthiazoles with n-BuLi at −78°C in THF, add to ketones or imines affording in ‘one-pot’ oxiranes and aziridines in a Z stereoselective manner. 相似文献
86.
Wojciech Dmowski Anna Ja?mu?na Z. Urbańczyk-Lipkowska 《Journal of fluorine chemistry》2007,128(12):1431-1438
Sodium dithionite effectively promotes the addition of dibromodifluoromethane to the exocyclic double bond of β-pinene. The reaction proceeded in a MeCN/H2O system to give almost quantitatively an adduct, 1-(2-bromo-2,2-difluoroethyl)-4-(2-bromoisopropyl)-cyclohexene, as the sole product. On treatment of the adduct with 2,2,6,6-tetramethylpiperidine elimination of HBr only from the (CH3)2CHBr group occurred to give a mixture of regioisomeric dienes, while treatment with 50% KOH under phase transfer catalysis conditions or with K2CO3 in DMF resulted in total dehydrobromination to give trienes possessing an exocyclic CHCF2 group. Surprisingly, the main course of the reactions of the adduct with DBU (1,8-diazabicyclo[5.4.0]undece-7-ene) and also with t-BuOK in THF was elimination of HBr only from the CH2CF2Br group to afford 1-(2,2-difluorovinyl)-4-(2-bromoisopropyl)cyclohexene as the main product. Catalytic hydrogenation of the adduct followed by treatment with DBU afforded a conjugated diene, 1-(2,2-difluorovinyl)-4-isopropylcyclohexene. Compounds bearing the CHCF2 group are new 1,1-difluorodienes which readily reacted with 4-phenyl-3H-1,2,4-triazoline-3,5-dione to give cycloadducts, derivatives of triazolo[1,2-α]cinnoline. 相似文献
87.
Compound CpMoI2(iPr2dad) (iPr2dad = iPrNCHCHNiPr), obtained by halide exchange from CpMoCl2(iPr2dad) and NaI, has been isolated and characterized by EPR spectroscopy, cyclic voltammetry, and X-ray crystallography. Its action as a catalyst in atom transfer radical polymerization (ATRP) and as a spin trap in organometallic radical polymerization (OMRP) of styrene and methyl acrylate (MA) monomers has been investigated and compared with that of the dichloro analogue. Compound CpMoCl2(iPr2dad) catalyzes the ATRP of styrene and MA with low efficiency factors f (as low as 0.37 for MA and ethyl 2-chloropropionate as initiator), while it irreversibly traps the corresponding growing radical chains under OMRP conditions. On the other hand, compound CpMoI2(iPr2dad) has a greater ATRP catalytic activity than the dichloro analogue and yields f = 1 for MA and ethyl 2-iodopropionate as initiator. Under OMRP conditions, it does not irreversibly trap the growing radical chains. This comparison serves to illustrate the general principle that low initiator efficiency factors, sometimes observed in ATRP, may result from the interplay of the ATRP and OMRP mechanisms, when the latter ones involves an irreversible radical trapping process. 相似文献
88.
罗登柏 《高等学校化学学报》1989,10(9):971
格兰图在离子选择电极法中应用广泛,但该图要求电极响应的能斯特斜率为一定值。对电极斜率偏离理论值的情况进行修正已有报道。 本文提出一种不需任何电极斜率校正步骤的算图,即以加入标准溶液后电位的变化值△E与实际斜率S的比值△pe对加入标准溶液体积Vs作图的计算图(简称为△pe格兰图)。在实际操作中,根据测得的△E值和S值,经换算为△pe后,即可在标准算图上作图进行结果计算。克服了作空白溶液线或共线图线时可能引进的误差,简化了结果处理过程。此外,对不同价态离子的测定,该算图纵坐标标度△pe不变,不必扩大或缩小,作图十分方便。 相似文献
89.
Starting from the readily available 4‐methylbenzoic acid, an efficient protocol for the preparation of ethyl 4‐(aminomethyl) benzyl (methyl) phosphinate ( 1 ), a novel aminomethylmonoalkylphosphinate was reported in this communication. The important step involves the selective monochlorination of phosphonic ester by POCl3 and forming the phosphonochloridate, and followed by nucleophilic addition of CH3MgBr to the acid chloride intermediate. 相似文献
90.
Prashanth Thodupunuri Marumamula Hanumaiah Shobanbabu Bommagani Gangavaram V. M. Sharma 《Journal of carbohydrate chemistry》2017,36(2-3):100-110
An efficient and short stereoselective synthesis of C11–C19 fragment of Macrolactin 3 was achieved. The vic-triol moiety (C15–C17) was derived from the C2–C4 chiral centers of D-mannose. The C-1 of D-mannose was utilized for the Wittig-olefination followed by hydroxylation using hydroboration reaction to introduce C11–C13 carbon chain in the C11–C19 fragment, whereas C5–C6 carbon chain of mannose was converted into C18–C19 of the target by dehydration reactions. Thus, the main strategy was (a) two consecutive Wittig-olefination reactions on C1 carbon of mannose, (b) inversion of C4 stereocenter, and (c) dehydration of C5–C6 vic-diol to olefin to result in the C11–C19 fragment. 相似文献