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1.
《中国化学》2018,36(7):587-593
An organocatalytic approach for direct conversion of racemic diarylmethanols to valuable chiral diarylmethylamines is described. Different from the previously reported elegant “borrowing hydrogen” approach, the present process employs a distinct complementary formal SN1 strategy. This approach enjoys excellent enantioselectivity, mild conditions, broad scope, and easy product derivatization. Mechanistically, control experiments also provided important insights into some notable features, such as substrate kinetic resolution and reversibility as well as the critical role of the ortho‐ hydroxy group in the substrate. 相似文献
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Synergistic Kinetic Resolution and Asymmetric Propargyl Claisen Rearrangement for the Synthesis of Chiral Allenes 下载免费PDF全文
Yangbin Liu Prof. Dr. Xiaohua Liu Haipeng Hu Jing Guo Yong Xia Dr. Lili Lin Prof. Dr. Xiaoming Feng 《Angewandte Chemie (International ed. in English)》2016,55(12):4054-4058
The asymmetric propargyl Claisen rearrangement provides a convenient entry to chiral allene motifs. Herein, we describe the development of a kinetic resolution and asymmetric rearrangement of racemic propargyl vinyl ethers. This transformation afforded chiral allene products along with the enantiomerically enriched substrate in good yields with excellent diastereo‐ and enantioselectivity. The complete chirality transfer and facially selective rearrangement enabled the simultaneous construction of an axially chiral allenic unit and a quaternary carbon stereocenter. 相似文献
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Dr. Xingguang Li Prof. Jianwei Sun 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17197-17202
An organocatalytic enantioconvergent synthesis of chiral tetrasubstituted allenes is disclosed. With suitable chiral phosphoric acid catalysts, a range of racemic indole-substituted propargylic alcohols reacted with nucleophiles to provide efficient access to a series of enantioenriched allenes with high enantioselectivities. Control experiments suggested a mechanism involving remotely controlled asymmetric 1,8-addition of the in situ generated indole imine methide via a bifunctional transition state. 相似文献
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Copper‐Catalyzed Propargylic Substitution of Dichloro Substrates: Enantioselective Synthesis of Trisubstituted Allenes and Formation of Propargylic Quaternary Stereogenic Centers 下载免费PDF全文
Dr. Hailing Li Dr. David Grassi Dr. Laure Guénée Prof. Dr. Thomas Bürgi Prof. Dr. Alexandre Alexakis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16694-16706
An easy and versatile Cu‐catalyzed propargylic substitution process is presented. Using easily prepared prochiral dichloro substrates, readily available Grignard reagents together with catalytic amount of copper salt and chiral ligand, we accessed a range of synthetically interesting trisubstituted chloroallenes. Substrate scope and nucleophile scope are broad, providing generally high enantioselectivity for the desired 1,3‐substitution products. The enantioenriched chloroallenes could be further transformed into the corresponding trisubstituted allenes or terminal alkynes bearing all‐carbon quaternary stereogenic centers, through the copper‐catalyzed enantiospecific 1,1/1,3‐substitutions. The two successive copper‐catalyzed reactions could be eventually combined into a one‐pot procedure and different desired allenes or alkynes were obtained respectively with high enantiomeric excesses. 相似文献
5.
An organocatalytic enantioconvergent synthesis of chiral tetrasubstituted allenes is disclosed. With suitable chiral phosphoric acid catalysts, a range of racemic indole‐substituted propargylic alcohols reacted with nucleophiles to provide efficient access to a series of enantioenriched allenes with high enantioselectivities. Control experiments suggested a mechanism involving remotely controlled asymmetric 1,8‐addition of the in situ generated indole imine methide via a bifunctional transition state. 相似文献
6.
Michael Addition Catalyzed by Chiral Secondary Amine Phosphoramide Using Fluorinated Silyl Enol Ethers: Formation of Quaternary Carbon Stereocenters 下载免费PDF全文
Jin‐Sheng Yu Fu‐Min Liao Wei‐Ming Gao Kui Liao Run‐Lin Zuo Prof. Dr. Jian Zhou 《Angewandte Chemie (International ed. in English)》2015,54(25):7381-7385
A chiral secondary amine phosphoramide was developed and identified as a powerful catalyst for the Mukaiyama–Michael addition of fluorinated enol silyl ethers to tetrasubstituted olefins. The resulting products are obtained with high enantioselectivities and contain a quaternary carbon stereocenter bearing either a difluoroalkyl or monofluoroalkyl group. 相似文献
7.
Dr. Aurélien Tap Dr. Aurélie Blond Dr. Vijay N. Wakchaure Prof. Dr. Benjamin List 《Angewandte Chemie (International ed. in English)》2016,55(31):8962-8965
Herein we describe the development of a catalytic enantioselective alkynylogous Mukaiyama aldol reaction. The reaction is catalyzed by a newly designed chiral disulfonimide and delivers chiral allenoates in high yields and with excellent regio‐, diastereo‐, and enantioselectivity. Our process tolerates a broad range of aldehydes in combination with diverse alkynyl‐substituted ketene acetals. The reaction products can be readily derivatized to furnish a variety of highly substituted enantiomerically enriched building blocks. 相似文献
8.
Atom‐Economic,Regiodivergent, and Stereoselective Coupling of Imidazole Derivatives with Terminal Allenes 下载免费PDF全文
Kun Xu Niels Thieme Prof. Dr. Bernhard Breit 《Angewandte Chemie (International ed. in English)》2014,53(8):2162-2165
New Rh‐ and Pd‐catalyzed regiodivergent and stereoselective intermolecular coupling reactions of imidazole derivatives with mono‐substituted allenes are herein reported. Using a RhI/Josiphos system, perfect regioselectivities and high enantiomeric excess were obtained, while a PdII/dppf system gave linear products with high regioselectivities and high E/Z selectivities. This method permits the atom economic synthesis of valuable branched and linear allylic imidazole derivatives. 相似文献
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Palladium‐Catalyzed Decarboxylative γ‐Arylation for the Synthesis of Tetrasubstituted Chiral Allenes
Ina Scheipers Christian Mück‐Lichtenfeld Armido Studer 《Angewandte Chemie (International ed. in English)》2019,58(20):6545-6548
An enantiospecific palladium‐catalyzed decarboxylative coupling of acyclic β,γ‐alkynoic acids with various aryl iodides to chiral tetrasubstituted allenes is described. The coupling reaction comprises a decarboxylative γ‐palladation of α,α‐disubstituted carboxylic acids to provide the tetrasubstituted allenes with complete point‐to‐axial chirality transfer in excellent yields. 相似文献
11.
Recent progress in asymmetric organocatalysis has led to the development of several asymmetric transformations that employ various substrates. Among these substrates, maleimides have emerged as excellent Michael acceptors, dienophiles, and dipolarophiles. In this Focus Review we highlight the advances in the asymmetric synthesis of succinimide derivatives through asymmetric organocatalytic addition reactions of maleimides. 相似文献
12.
Indoles are one of the most ubiquitous subclass of N-heterocycles and are increasingly incorporated to design new axially chiral scaffolds. The rich profile of reactivity and N−H functionality allow chemical derivatization for enhanced medicinal, material and catalytic properties. Although asymmetric C−C coupling of two arenes gives the most direct access of axially chiral biaryl scaffolds, this chemistry has been the remit of metal catalysis and works efficiently on limited substrates. Our group has devoted special interest in devising novel organocatalytic arylation reactions to fabricate biaryl atropisomers. In this realm, indoles and derivatives have been reliably used as the arylation partners in combination with azoarenes, nitrosonapthalenes and quinone derivatives. Their efficient interaction with chiral phosphoric acid catalyst as well as the tunability of electronics and sterics have enabled excellent control of stereo-, chemo- and regioselectivity to furnish diverse scaffolds. In addition, indoles could act as nucleophiles in desymmetrization of 1,2,4-triazole-3,5-diones. This account provides a succinct illustration of these developments. 相似文献
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Jia Qiu Shen Gao Chaopeng Li Dr. Lei Zhang Prof. Dr. Zheng Wang Dr. Xiaoming Wang Prof. Dr. Kuiling Ding 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(61):13874-13878
A catalytic enantioselective construction of all-carbon chiral quaternary centers through reductive hydroxymethylation of 1,1-disubstituted allenes with CO2 has been developed. In the presence of a copper/Mandyphos catalyst, CO2 is transformed into an alcohol oxidation level by an asymmetric reductive C−C bond formation with allenes by using hydrosilane (HSi(OMe)2Me) as a reductant. The resulting chiral homoallylic alcohols are versatile synthetic intermediates and can be conveniently converted into a variety of useful chiral chemicals. 相似文献
17.
Counterion‐Induced Asymmetric Control in Ring‐Opening of Azetidiniums: Facile Access to Chiral Amines 下载免费PDF全文
Dr. Deyun Qian Dr. Min Chen Dr. Alex C. Bissember Prof. Jianwei Sun 《Angewandte Chemie (International ed. in English)》2018,57(14):3763-3766
Counterion‐induced stereocontrol is a powerful tool in organic synthesis. However, such enantiocontrol on tetrahedral ammonium cations remains challenging. Described here is the first example of using chiral anion phase‐transfer catalysis to achieve intermolecular ring‐opening of azetidiniums with excellent enantioselectivity (up to 97 % ee). Precise control over the formation and reaction of the chiral ion pair as well as inhibition of the background reaction by the biphasic system is key to the success of the reaction. 相似文献
18.
James P. Phelan Evan J. Patel Prof. Dr. Jonathan A. Ellman 《Angewandte Chemie (International ed. in English)》2014,53(42):11329-11332
The first example of a catalytic enantioselective addition to and nitronate protonation of trisubstituted nitroalkenes to produce highly enantioenriched products with a tetrasubstituted carbon is reported. Thioacids added in excellent yields and with high enantioselectivities to both activated and unactivated nitroalkenes. The 1,2‐nitrothioacetate products can be readily converted in two steps to biomedically relevant 1,2‐aminosulfonic acids without loss of enantiopurity. 相似文献
19.
手性胺-质子酸是近年来发展起来的新型高效、高对映选择性的有机催化体系, 已成功应用于催化不对称Aldol反应、Michael加成反应、Diels-Alder反应和Strecker反应等许多重要的有机合成反应. 价廉易得的质子酸的引入不仅可促进活性中间体烯胺的生成, 并可通过形成的氢键稳定反应的过渡态, 从而显著提高该催化体系的催化活性和立体选择性. 对各类手性胺-质子酸催化剂在有机催化不对称合成反应中的应用、不对称诱导反应的机理、手性胺和质子酸的分子结构对其催化活性和不对称诱导活性的影响进行了评述. 相似文献
20.
Efficient Synthesis of Chiral Trisubstituted 1,2‐Allenyl Ketones by Catalytic Asymmetric Conjugate Addition of Malonic Esters to Enynes 下载免费PDF全文
Qian Yao Yuting Liao Dr. Lili Lin Xiaobin Lin Jie Ji Prof. Dr. Xiaohua Liu Prof. Dr. Xiaoming Feng 《Angewandte Chemie (International ed. in English)》2016,55(5):1859-1863
An N,N′‐dioxide/scandium(III) complex catalyzed, highly efficient conjugate addition of malonic esters to enynes is described. A range of trisubstituted 1,2‐allenyl ketones were obtained in high yields (up to 99 %) with good d.r. (up to 95/5) and excellent ee values (97 %–99 %). Moreover, the products could be easily transformed into chiral furan and 5‐hydroxypyrazoline derivatives, both of which are important skeletons of many biologically active compounds and pharmacologicals. 相似文献