共查询到20条相似文献,搜索用时 15 毫秒
1.
Hanyang Bao Dr. Yunrong Chen Prof. Dr. Xiaoyu Yang 《Angewandte Chemie (International ed. in English)》2023,62(14):e202300481
Axially chiral diaryl ethers are a type of unique atropisomers bearing two potential axes, which have potential applications in a variety of research fields. However, the catalytic enantioselective synthesis of these diaryl ether atropisomers is largely underexplored when compared to the catalytic asymmetric synthesis of biaryl or other types of atropisomers. Herein, we report a highly efficient catalytic asymmetric synthesis of diaryl ether atropisomers through an organocatalyzed enantioselective desymmetrization protocol. The chiral phosphoric acid-catalyzed asymmetric electrophilic aromatic aminations of the symmetrical 1,3-benzenediamine type substrates afforded a series of diaryl ether atropisomers in excellent yields and enantioselectivities. The facile construction of heterocycles by the utilizations of the 1,2-benzenediamine moiety in the products provided access to a variety of structurally diverse and novel azaarene-containing diaryl ether atropisomers. 相似文献
2.
Binghui Wang Yilin Liu Chenyang Jiang Zheng Cao Dr. Shanshan Cao Dr. Xiaowei Zhao Dr. Xu Ban Dr. Yanli Yin Prof. Dr. Zhiyong Jiang 《Angewandte Chemie (International ed. in English)》2023,62(16):e202216605
A chiral Brønsted acid-catalysed asymmetric hydrophosphinylation of 2-vinylazaarenes by secondary phosphine oxides is described. A variety of P-chiral 2-azaaryl-ethylphosphine oxides are synthesized with high yields and ees, of which both the substituents of phosphines and azaarenes can be flexibly modulated, underscoring an exceptionally broad scope of substrates. These adducts are valuable to asymmetric metal catalysis since the resultant P-chiral tertiary phosphines from the reduction of them are verified as a kind of effective C1-symmetric chiral 1,5-hybrid P,N-ligands. Importantly, this catalysis platform enables the generic and efficient kinetic resolution of P-chiral secondary phosphine oxides. It thus provides an expedient approach to access the enantiomers of the P-chiral tertiary phosphine oxides derived from asymmetric hydrophosphinylation, further improving the utility of the method. 相似文献
3.
Linlong Dai Yuheng Liu Qing Xu Meifang Wang Dr. Qiaohong Zhu Prof. Dr. Peiyuan Yu Prof. Dr. Guofu Zhong Prof. Dr. Xiaofei Zeng 《Angewandte Chemie (International ed. in English)》2023,62(7):e202216534
Diaryl ethers are widespread in biologically active compounds, ligands and catalysts. It is known that the diaryl ether skeleton may exhibit atropisomerism when both aryl rings are unsymmetrically substituted with bulky groups. Despite recent advances, only very few catalytic asymmetric methods have been developed to construct such axially chiral compounds. We describe herein a dynamic kinetic resolution approach to axially chiral diaryl ethers via a Brønsted acid catalyzed atroposelective transfer hydrogenation (ATH) reaction of dicarbaldehydes with anilines. The desired diaryl ethers could be obtained in moderate to good chemical yields (up to 79 %) and high enantioselectivities (up to 95 % ee) under standard reaction conditions. Such structural motifs are interesting precursors for further transformations and may have potential applications in the synthesis of chiral ligands or catalysts. 相似文献
4.
Oleg I. Kolodiazhnyi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8-9):2111-2114
New examples of multistereoselective syntheses of organophosphorus compounds are described. 相似文献
5.
Panjie Hu Lingfei Hu Dr. Xiao-Xi Li Mengxiao Pan Dr. Gang Lu Prof. Dr. Xingwei Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(1):e202312923
Axially chiral open-chained olefins are an underexplored class of atropisomers, whose enantioselective synthesis represents a daunting challenge due to their relatively low racemization barrier. We herein report rhodium(I)-catalyzed hydroarylative cyclization of 1,6-diynes with three distinct classes of arenes, enabling highly enantioselective synthesis of a broad range of axially chiral 1,3-dienes that are conformationally labile (ΔG≠(rac)=26.6–28.0 kcal/mol). The coupling reactions in each category proceeded with excellent enantioselectivity, regioselectivity, and Z/E selectivity under mild reaction conditions. Computational studies of the coupling of quinoline N-oxide system reveal that the reaction proceeds via initial oxidative cyclization of the 1,6-diyne to give a rhodacyclic intermediate, followed by σ-bond metathesis between the arene C−H bond and the Rh−C(vinyl) bond, with subsequent C−C reductive elimination being enantio-determining and turnover-limiting. The DFT-established mechanism is consistent with the experimental studies. The coupled products of quinoline N-oxides undergo facile visible light-induced intramolecular oxygen-atom transfer, affording chiral epoxides with complete axial-to-central chirality transfer. 相似文献
6.
Yang-Bo Chen Li-Gao Liu Can-Ming Chen Yi-Xi Liu Prof. Dr. Bo Zhou Xin Lu Zhou Xu Prof. Dr. Long-Wu Ye 《Angewandte Chemie (International ed. in English)》2023,62(23):e202303670
Axially chiral biaryls widely exist in natural products and pharmaceuticals and are used as chiral ligands and catalysts in asymmetric synthesis. Compared to the well-established axially chiral 6-membered biaryl skeletons, examples of 5-membered biaryls have been quite scarce, and mono-substituted 3-arylpyrrole atropisomers have not been reported. Here, we disclose a copper-catalyzed atroposelective diyne cyclization for the construction of a range of axially chiral arylpyrrole biaryls in good to excellent yields with generally excellent enantioselectivities via oxidation and X−H insertion of vinyl cations. Importantly, this protocol not only represents the first synthesis of mono-substituted 3-arylpyrrole atropisomers, but also constitutes the first example of atroposelective diyne cyclization and the first atropisomer construction via vinyl cations. Theoretical calculations further support the mechanism of vinyl cation-involved cyclization and elucidate the origin of enantioselectivity. 相似文献
7.
Soumyadeep Chakrabortty Katharina Konieczny Felix J. de Zwart Dr. Eduard. O. Bobylev Dr. Eszter Baráth Dr. Sergey Tin Dr. Bernd H. Müller Prof. Dr. Joost N. H. Reek Prof. Dr. Bas de Bruin Prof. Dr. Johannes G. de Vries 《Angewandte Chemie (International ed. in English)》2023,62(26):e202301329
The enantioselective hydrogenation of cyclic enamides has been achieved using an earth-abundant cobalt-bisphosphine catalyst. Using CoCl2/(S,S)-Ph-BPE, several trisubstituted carbocyclic enamides were reduced with high activity and excellent enantioselectivity (up to 99 %) to the corresponding saturated amides. The methodology can be extended to the synthesis of chiral amines by base hydrolysis of the hydrogenation products. Preliminary mechanistic investigations reveal the presence of a high spin cobalt (II) species in the catalytic cycle. We propose that the hydrogenation of the carbon-carbon double bond proceeds via a sigma-bond-metathesis pathway. 相似文献
8.
Jian Zhou Dr. Ling Meng Dr. Shujuan Lin Baohua Cai Prof. Jun Wang 《Angewandte Chemie (International ed. in English)》2023,62(26):e202303727
Transition metal-catalyzed hydrofunctionalization of methylenecyclopropanes (MCPs) has presented a considerable challenge due to the difficult manipulation of regioselectivity and complicated reaction patterns. Herein, we report a straightforward Pd-catalyzed ring-opening hydrophosphinylation reaction of MCPs via highly selective C−C bond cleavage. This method allows for rapid and efficient access to a wide range of chiral allylic phosphine oxides in good yields and high enantioselectivities. Additionally, density functional theory (DFT) calculations were performed to elucidate the reaction mechanism and the origin of enantioselectivity. 相似文献
9.
Dr. Junning Kou Dr. Qi Wu Dr. Dongxu Cui Dr. Yun Geng Dr. Kunhao Zhang Prof. Dr. Min Zhang Prof. Dr. Hongying Zang Prof. Dr. Xinlong Wang Prof. Dr. Zhongmin Su Prof. Dr. Chunyi Sun 《Angewandte Chemie (International ed. in English)》2023,62(47):e202312733
Chiral induction has been an important topic in chemistry, not only for its relevance in understanding the mysterious phenomenon of spontaneous symmetry breaking in nature but also due to its critical implications in medicine and the chiral industry. The induced chirality of fullerenes by host–guest interactions has been rarely reported, mainly attributed to their chiral resistance from high symmetry and challenges in their accessibility. Herein, we report two new pairs of chiral porous aromatic cages (PAC), R- PAC-2 , S- PAC-2 (with Br substituents) and R- PAC-3 , S- PAC-3 (with CH3 substituents) enantiomers. PAC-2 , rather than PAC-3 , achieves fullerene encapsulation and selective binding of C70 over C60 in fullerene carbon soot. More significantly, the occurrence of chiral induction between R- PAC-2 , S- PAC-2 and fullerenes is confirmed by single-crystal X-ray diffraction and the intense CD signal within the absorption region of fullerenes. DFT calculations reveal the contribution of electrostatic effects originating from face-to-face arene-fullerene interactions dominate C70 selectivity and elucidate the substituent effect on fullerene encapsulation. The disturbance from the differential interactions between fullerene and surrounding chiral cages on the intrinsic highly symmetric electronic structure of fullerene could be the primary reason accounting for the induced chirality of fullerene. 相似文献
10.
Peng-Ying Jiang Dr. San Wu Dr. Guan-Jun Wang Dr. Shao-Hua Xiang Prof. Dr. Bin Tan 《Angewandte Chemie (International ed. in English)》2023,62(40):e202309272
QUINAPs have emerged as a pivotal class of axially chiral compounds with remarkable features in the stereoinduction of diverse enantioselective transformations. However, the confined substrate range and extravagant price still pose challenges, limiting their broader utilization. Herein, we describe the first atroposelective oxidation of an N atom using a chiral ketone catalyst, allowing the kinetic resolution of QUINAPOs to give both the unreacted substrates and their corresponding N-oxides with excellent enantioselectivity. Importantly, the enantioenriched products can be readily converted into the QUINAP targets without any loss of stereochemical integrity. Mechanistic investigations indicate that a dioxirane, generated through the oxidation of the ketone with oxone, acts as the active catalytic species. Furthermore, we have successfully extended this catalytic system to the kinetic resolution of QUINOLs and the dynamic kinetic transformation of pyridine analogues of QUINAPO possessing a labile stereogenic axis. The practicality of the developed protocol is further demonstrated by the successful application of QUINAPO N-oxide as a Lewis base catalyst in a series of enantioselective transformations. 相似文献
11.
Shibaram Panda Prof. Dr. Prasanta Ghorai 《Angewandte Chemie (International ed. in English)》2023,62(32):e202306179
Leveraging the unexplored regions of chemical space, the integration of spirocyclic cyclobutane in a molecular scaffold opens up a new vista in modern drug discovery. Despite recent advancements in achieving the synthesis of such motifs, strategies for their asymmetric construction have not been well-recognized and remain a formidable challenge. Herein, for the first time, we have demonstrated a chiral Brønsted acid-catalyzed enantioselective synthesis of 1-azaspiro cyclobutanone enabled by an unusual reactivity of enamine that explore the potentiality of Heyns rearrangement upon electrophilic modification. This design strategy offers viable access to a wide range of cyclobutanone containing spiroindoline and spiropyrrolidine derivatives in good yields with excellent stereoselectivities (up to >99 % ee, >20 : 1 dr). Furthermore, the practicality of this methodology has been shown by a scale-up synthesis of spirocyclic products and their facile post-synthetic modifications. 相似文献
12.
Qimin Wu Qi Zhang Shuxin Yin Prof. Dr. Aijun Lin Dr. Shang Gao Prof. Dr. Hequan Yao 《Angewandte Chemie (International ed. in English)》2023,62(30):e202305518
Hydrofunctionalization of alkynes is one of the most efficient ways to access axially chiral styrenes with open-chained olefins. While great advances have been achieved for 1-alkynylnaphthalen-2-ols and analogues, atroposelective hydrofunctionalization of unactivated internal alkynes lags. Herein we reported a platinum-catalyzed atroposelective hydrosilylation of unactivated internal alkynes for the first time. With monodentate TADDOL-derived phosphonite L1 used as a chiral ligand, various axially chiral styrenes were achieved in excellent enantioselectivities with high E-selectivities. Control experiments showed that the NH-arylamide groups have significant effects on both the yields and enantioselectivities and could act as directing groups. The potential utilities of the products were shown by the transformations of the amide motifs of the products. 相似文献
13.
Rongyu Sun Emilie Viaud Dr. Rajesh Nomula Dr. Jean-Valère Naubron Dr. Nicolas Daugey Dr. Thierry Buffeteau Prof. Frédéric Castet Prof. Patrick Y. Toullec Prof. Stéphane Quideau Dr. Philippe A. Peixoto 《Angewandte Chemie (International ed. in English)》2023,62(42):e202310436
The reactivity of novel chiral lactamide-substituted diselenide-based reagents under oxidative conditions was exploited to develop a metal-free method for the preparation of enantioenriched allenylamides from simple alkynes in good yields, and with enantiomeric excesses up to 99 %. The key of the success in this method is attributed to the hydrogen-bonded lactamide appendages that ensure configurational stability of chiral vinyl selenoxide intermediates for an optimal enantiotopic β-syn-elimination step. 相似文献
14.
Jia-Yu Zou Yu-Ying Yang Jun Gu Fei Liu Dr. Zhiwen Ye Dr. Wenbin Yi Prof. Ying He 《Angewandte Chemie (International ed. in English)》2023,62(40):e202310320
Axially chiral N-substituted quinazolinones are important bioactive molecules, which are presented in many synthetic drugs. However, most strategies toward their atroposelective synthesis are mainly limited to the axially chiral arylquinazolinone frameworks. The development of modular synthetic methods to access diverse quinazolinone-based atropisomers remains scarce and challenging. Herein, we report the regio- and atroposelective synthesis of axially chiral N-vinylquinazolinones via the strategy of asymmetric allylic substitution-isomerization. The catalysis system utilized both asymmetric transition-metal catalysis and organocatalysis to efficiently afford trisubstituted and tetrasubstituted N-vinylquinazolinone atropisomers, respectively. With the meticulous design of β-substituted allylic substrates, both Z- and E-tetrasubstituted axially chiral N-vinylquinazolinones were obtained in good yields and high enantioselectivities. 相似文献
15.
Xiang Li Gao-Wei Wang Li-Xia Liu Prof. Dr. Chang-Bin Yu Prof. Dr. Yong-Gui Zhou 《Angewandte Chemie (International ed. in English)》2023,62(16):e202301337
Here we report the first palladium-catalyzed asymmetric hydrogenolysis of readily available aryl triflates via desymmetrization and kinetic resolution for facile construction of axially chiral biaryl scaffolds with excellent enantioselectivities and s selectivity factors. The axially chiral monophosphine ligands could be prepared from these chiral biaryl compounds and were further applied to palladium-catalyzed asymmetric allylic alkylation with excellent ee values and high branched and linear ratio, which demonstrated the potential utility of this methodology. 相似文献
16.
Cong‐Shuai Wang Tian‐Zhen Li Si‐Jia Liu Yu‐Chen Zhang Shuang Deng Yinchun Jiao Feng Shi 《中国化学》2020,38(6):543-552
A new class of axially chiral aryl‐alkene‐indole frameworks have been designed, and the first catalytic asymmetric construction of such scaffolds has been established by the strategy of organocatalytic (Z/E)‐selective and enantioselective (4+3) cyclization of 3‐alkynyl‐2‐indolylmethanols with 2‐naphthols or phenols (all >95 : 5 E/Z, up to 98% yield, 97% ee). This reaction also represents the first catalytic asymmetric construction of axially chiral alkene‐heteroaryl scaffolds, which will add a new member to the atropisomeric family. This approach has not only confronted the great challenges in constructing axially chiral alkene‐heteroaryl scaffolds but also provided a powerful strategy for the enantioselective construction of axially chiral aryl‐alkene‐indole frameworks. 相似文献
17.
In order to model the asymmetric active site of the type‐3 copper enzyme tyrosinase the “doubly asymmetric” binucleating ligand 1‐[bis‐N,N‐(pyrid‐2‐ylmethyl)aminomethyl]‐3‐[N‐(pyrid‐2‐ylmethyl)‐N‐(2‐pyrid‐2‐ylethyl)aminomethyl]benzene (“unsDMPA”) is synthesized and coordinated to copper(I). The O2‐reactivity of the CuI(unsDMPA) complex and its analog derived from the symmetric counterpiece of unsDMPA, DMPA, is investigated. Oxygenation in methanol leads to dicopper(II) bis(μ‐hydroxo) and bis(μ‐methanolato) complexes; the dicopper(II) bis(μ‐hydroxo) complex of the unsDMPA ligand is chiral. Oxygenation in dichloromethane leads to oxidative N‐dealkylation. This is attributed to a tendency of DMPA and unsDMPA complexes to form dicopper bis(μ‐oxo) intermediates, as evidenced by DFT. The implications of these results with respect to the design of tyrosinase model systems are discussed. 相似文献
18.
Kun Wang Lin Zhang Weijun Tang Huaming Sun Dong Xue Ming Lei Jianliang Xiao Chao Wang 《Angewandte Chemie (International ed. in English)》2020,59(28):11408-11415
The first example of an asymmetric Guerbet reaction has been developed. Using commercially available, classic Noyori RuII‐diamine‐diphosphine catalysts, well‐known in asymmetric hydrogenation, racemic secondary alcohols are shown to couple with primary alcohols in the presence of a base, affording new chiral alcohols with enantiomeric ratios of up to 99:1. Requiring no reducing agents, the protocol provides an easy, alternative route for the synthesis of chiral alcohols. Mechanistic studies reveal that the reaction proceeds via a Ru‐catalyzed asymmetric hydrogen autotransfer process in concert with a base‐promoted allylic alcohol isomerization. 相似文献
19.
Dr. Lingling Zhang Yilin Chen Dr. Jiapeng Zheng Dr. George R. Lewis Xinyue Xia Prof. Emilie Ringe Prof. Wei Zhang Prof. Jianfang Wang 《Angewandte Chemie (International ed. in English)》2023,62(52):e202312615
Chiral plasmonic nanoparticles have attracted much attention because of their strong chiroptical responses and broad scientific applications. However, the types of chiral plasmonic nanoparticles have remained limited. Herein we report on a new type of chiral nanoparticle, chiral Au nanorod (NR) with five-fold rotational symmetry, which is synthesized using chiral molecules. Three different types of Au seeds (Au elongated nanodecahedrons, nanodecahedrons, and nanobipyramids) are used to study the growth behaviors. Different synthesis parameters, including the chiral molecules, surfactant, reductant, seeds, and Au precursor, are systematically varied to optimize the chiroptical responses of the chiral Au NRs. The chiral scattering measurements on the individual chiral Au NRs and their dimers are performed. Intriguingly, the chiroptical signals of the individual chiral Au NRs and their end-to-end dimers are similar, while those of the side-by-side dimers are largely reduced. Theoretical calculations and numerical simulations reveal that the different chiroptical responses of the chiral NR dimers are originated from the coupling effect between the plasmon resonance modes. Our study enriches chiral plasmonic nanoparticles and provides valuable insight for the design of plasmonic nanostructures with desired chiroptical properties. 相似文献
20.
手性磷酸在不对称反应中的应用 总被引:1,自引:0,他引:1
手性磷酸催化剂因其在不对称催化反应中表现出的高效、高对映选择性而受到人们越来越多的关注.含1,1'-联二萘酚(BINOL)骨架的手性磷酸类催化剂已被广泛用于亚胺的不对称氢转移、Friedel-Crafts反应和Mannich反应等许多重要的有机合成反应.手性磷酸具有同时提供质子和接受质子的双功能作用,因此可以同时活化两个反应底物.含BINOL骨架的手性磷酸可以通过改变BINOL骨架3,3'-位上的取代基调控空间位阻和手性磷酸的酸性,因此可以调节反应的对映选择性.为了合理地设计新的手性磷酸催化剂,扩大其应用范围,最近人们对手性磷酸不对称催化反应机理进行了初步的理论计算研究并取得了显著进展.综述了手性磷酸在不对称反应中的部分研究工作,尤其是理论研究领域的最新成果. 相似文献