化学专业英语摘要翻译6篇汇编
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Asymmetric C(sp)-C(sp2) bond formation to give enantiomerically enriched
1,3-butadienyl-2-carbinols occurred through a homoallenylboration reaction between a 2,3-dienylboronic ester and aldehydes under the catalysis of a chiral phosphoric acid (CPA). A diverse range of enantiomerically enriched butadiene-substituted secondary alcohols with aryl,heterocyclic, and aliphatic substituents were synthesized in very high yield with high enantioselectivity. Preliminary density functional theory (DFT) calculations suggest that the reaction proceeds via a cyclic six-membered chairlike transition state with essential hydrogen-bond activation in the allene reagent.The catalytic reaction was amenable to the gram-scale synthesis of a chiral alkyl butadienyl adduct, which was converted into an interesting optically pure compound bearing a benzo-fused spirocyclic cyclopentenone framework.
在手性磷酸(CPA)催化剂条件下,2,3-硼酸酯和醛通过反应生成了富对映体的1,3-丁二烯-2-甲醇,这里面含有不对称的碳(sp杂化)碳(sp2杂化)键。不同丁二烯取代的二级醇的富对映体和芳香烃、杂环以及脂肪烃的合成可以有高产率和很好的对映体选择性。初步的密度泛函理论(DFT)的计算表明,这个反应是在丙二醇试剂中通过对氢键必要的活化而经过了一个六元环椅型结构的过渡态实现的。这个反应对于手性的烷基二烯的克级别反应而言是容易控制的,而手性的烷基二烯可以转化为一种有趣的耐苯并环戊酮的光学纯化合物。
Yiyong Huang,Xing Yang, Zongchao Lv,Chen Cai,Cheng Kai, Yong Pei,and Yu Feng. Asymmetric Synthesis of 1,3-Butadienyl-2-carbinols by the Homoallenylboration of Aldehydes with a Chiral Phosphoric Acid Catalyst[J].Angewandte
Chemie,2015,127:7407-7410
C-H bonds are ubiquitous in organic compounds. It would, therefore, appear that direct functionalization of substrates by activation of C-H bonds would eliminate the multiple steps and limitations associated with the preparation of functionalized starting materials. Regioselectivity is an important issue because organic molecules can contain a wide variety of C-H bonds. The use of a directing group can largely overcome the issue of regiocontrol by allowing the catalyst to come into proximity with the targeted C-H bonds. A wide variety of functional groups have been evaluated for use as directing groups in the transformation of C-H bonds. In 2005, Daugulis reported the arylation of unactivated C(sp(3))-H bonds by using 8-aminoquinoline and picolinamide as bidentate directing groups, with Pd(OAc)2 as the catalyst. Encouraged by these promising results, a number of transformations of C-H bonds have since been developed by using systems based on bidentate directing groups. In this Review, recent advances in this area are discussed.
C-H键有机化合物中无处不在。这样看来,通过使用已活化C-H键的直接功能性底物可以消除与合成功能性原料有关的反应的多步数以及限制条件。区域选择性是一个重要的问题,因为有机分子含有多种多样的C-H键。而一种定向取代基可以使催化剂进入到目标C-H键的附近,这种定向取代基的使用可以很大程度上克服区域选择性的问题。在C-H键的转化中,作为定向基团的各种官能团已经被评估。在2005年,Daugulis报道通过利用8-氨基喹啉和吡啶酰胺作为双齿配位定向官能团,Pd(OAc)2作为催化剂,使未活化的C(sp3杂化)-H键发生芳基化反应。受这些好的实验结果的鼓舞,通过使用基于双齿定向基团的系统,许多C-H 键的转换已经被开发出来。在这篇评论中,对这方面的最新进展进行了讨论。
G Rouquet,N Chatani.Catalytic functionalization of C(sp2)-H and C(sp3)-H bonds by using bidentate directing groups[J]. Angewandte Chemie ,2013,52(45):11726-11743.