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1.
Asymmetric Radical–Radical Cross‐Coupling through Visible‐Light‐Activated Iridium Catalysis 下载免费PDF全文
Chuanyong Wang Jie Qin Xiaodong Shen Radostan Riedel Dr. Klaus Harms Prof. Dr. Eric Meggers 《Angewandte Chemie (International ed. in English)》2016,55(2):685-688
Combining single electron transfer between a donor substrate and a catalyst‐activated acceptor substrate with a stereocontrolled radical–radical recombination enables the visible‐light‐driven catalytic enantio‐ and diastereoselective synthesis of 1,2‐amino alcohols from trifluoromethyl ketones and tertiary amines. With a chiral iridium complex acting as both a Lewis acid and a photoredox catalyst, enantioselectivities of up to 99 % ee were achieved. A quantum yield of <1 supports the proposed catalytic cycle in which at least one photon is needed for each asymmetric C? C bond formation mediated by single electron transfer. 相似文献
2.
Asymmetric Ring‐Opening of Cyclopropyl Ketones with Thiol,Alcohol, and Carboxylic Acid Nucleophiles Catalyzed by a Chiral N,N′‐Dioxide–Scandium(III) Complex 下载免费PDF全文
Yong Xia Dr. Lili Lin Fenzhen Chang Xuan Fu Prof. Dr. Xiaohua Liu Prof. Dr. Xiaoming Feng 《Angewandte Chemie (International ed. in English)》2015,54(46):13748-13752
A highly efficient asymmetric ring‐opening reaction of cyclopropyl ketones with a broad range of thiols, alcohols and carboxylic acids has been first realized by using a chiral N,N′‐dioxide–scandium(III) complex as catalyst. The corresponding sulfides, ethers, and esters were obtained in up to 99 % yield and 95 % ee. This is also the first example of one catalytic system working for the ring‐opening reaction of donor–acceptor cyclopropanes with three different nucleophiles, let alone in an asymmetric version. 相似文献
3.
Yong Xia Lili Lin Fenzhen Chang Xuan Fu Xiaohua Liu Xiaoming Feng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(46):13952-13956
A highly efficient asymmetric ring‐opening reaction of cyclopropyl ketones with a broad range of thiols, alcohols and carboxylic acids has been first realized by using a chiral N,N′‐dioxide–scandium(III) complex as catalyst. The corresponding sulfides, ethers, and esters were obtained in up to 99 % yield and 95 % ee. This is also the first example of one catalytic system working for the ring‐opening reaction of donor–acceptor cyclopropanes with three different nucleophiles, let alone in an asymmetric version. 相似文献
4.
ZnCl2‐Promoted Asymmetric Hydrogenation of β‐Secondary‐Amino Ketones Catalyzed by a P‐Chiral Rh–Bisphosphine Complex 下载免费PDF全文
Qiupeng Hu Dr. Zhenfeng Zhang Prof. Yangang Liu Prof. Tsuneo Imamoto Prof. Wanbin Zhang 《Angewandte Chemie (International ed. in English)》2015,54(7):2260-2264
A new catalytic system has been developed for the asymmetric hydrogenation of β‐secondary‐amino ketones using a highly efficient P‐chiral bisphosphine–rhodium complex in combination with ZnCl2 as the activator of the catalyst. The chiral γ‐secondary‐amino alcohols were obtained in 90–94 % yields, 90–99 % enantioselectivities, and with high turnover numbers (up to 2000 S/C; S/C=substrate/catalyst ratio). A mechanism for the promoting effect of ZnCl2 on the catalytic system has been proposed on the basis of NMR spectroscopy and HRMS studies. This method was successfully applied to the asymmetric syntheses of three important drugs, (S)‐duloxetine, (R)‐fluoxetine, and (R)‐atomoxetine, in high yields and with excellent enantioselectivities. 相似文献
5.
Dr. Naifu Hu Hoimin Jung Yu Zheng Juhyeong Lee Dr. Lilu Zhang Zakir Ullah Dr. Xiulan Xie Dr. Klaus Harms Prof. Dr. Mu‐Hyun Baik Prof. Dr. Eric Meggers 《Angewandte Chemie (International ed. in English)》2018,57(21):6242-6246
A novel method for the catalytic asymmetric dearomatization by visible‐light‐activated [2+2] photocycloaddition with benzofurans and one example of a benzothiophene is reported, thereby providing chiral tricyclic structures with up to four stereocenters including quaternary stereocenters. The benzofurans and the benzothiophene are functionalized at the 2‐position with a chelating N‐acylpyrazole moiety which permits the coordination of a visible‐light‐activatable chiral‐at‐rhodium Lewis acid catalyst. Computational molecular modeling revealed the origin of the unusual regioselectivity and identified the heteroatom in the heterocycle to be key for the regiocontrol. 相似文献
6.
A Highly cis‐Selective and Enantioselective Metal‐Free Hydrogenation of 2,3‐Disubstituted Quinoxalines 下载免费PDF全文
Zhenhua Zhang Prof. Dr. Haifeng Du 《Angewandte Chemie (International ed. in English)》2015,54(2):623-626
A wide range of 2,3‐disubstituted quinoxalines have been successfully hydrogenated with H2 using borane catalysts to produce the desired tetrahydroquinoxalines in 80–99 % yields with excellent cis selectivity. Significantly, the asymmetric reaction employing chiral borane catalysts generated by the in situ hydroboration of chiral dienes with HB(C6F5)2 under mild reaction conditions has also been achieved with up to 96 % ee, and represents the first catalytic asymmetric system to furnish optically active cis‐2,3‐disubstituted 1,2,3,4‐tetrahydroquinoxalines. 相似文献
7.
Asymmetric Hydroalkoxylation of Non‐Activated Alkenes: Titanium‐Catalyzed Cycloisomerization of Allylphenols at High Temperatures 下载免费PDF全文
M. Sc. Johannes Schlüter M. Sc. Max Blazejak Dr. Florian Boeck Prof. Dr. Lukas Hintermann 《Angewandte Chemie (International ed. in English)》2015,54(13):4014-4017
The asymmetric catalytic addition of alcohols (phenols) to non‐activated alkenes has been realized through the cycloisomerization of 2‐allylphenols to 2‐methyl‐2,3‐dihydrobenzofurans (2‐methylcoumarans). The reaction was catalyzed by a chiral titanium–carboxylate complex at uncommonly high temperatures for asymmetric catalytic reactions. The catalyst was generated by mixing titanium isopropoxide, the chiral ligand (aS)‐1‐(2‐methoxy‐1‐naphthyl)‐2‐naphthoic acid or its derivatives, and a co‐catalytic amount of water in a ratio of 1:1:1 (5 mol % each). This homogeneous thermal catalysis (HOT‐CAT) gave various (S)‐2‐methylcoumarans with yields of up to 90 % and in up to 85 % ee at 240 °C, and in 87 % ee at 220 °C. 相似文献
8.
Ke Shen Xiaohua Liu Dr. Ke Zheng Wei Li Xiaolei Hu Lili Lin Dr. Xiaoming Feng Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(12):3736-3742
A direct catalytic asymmetric aldol‐type reaction of 3‐substituted‐2‐oxindoles with glyoxal derivatives and ethyl trifluoropyruvate, catalyzed by a chiral N,N′‐dioxide–Sc(OTf)3 (Tf=trifluoromethanesulfonyl) complex, has been developed that tolerates a wide range of substrates. The reaction proceeds in good yields and excellent enantioselectivities (up to 93 % yield, 99:1 diastereomeric ratio (dr), and >99 % enantiomeric excess (ee)) under mild conditions, to deliver 3‐(α‐hydroxy‐β‐carbonyl) oxindoles with vicinal quaternary–tertiary or quaternary–quaternary stereocenters. Even with 1 mol % catalyst loading or on scaleup (10 mmol of starting material), maintenance of ee was observed, which showed the potential value of the catalyst system. In studies probing the reaction mechanism, a positive nonlinear effect was observed and ScIII‐based enolate intermediates were detected by using ESIMS. On the basis of the experimental results and previous reports, a possible catalytic cycle was assumed. 相似文献
9.
Kai Zhang Liang‐Qiu Lu Yue Jia Ying Wang Fu‐Dong Lu Fangfang Pan Wen‐Jing Xiao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(38):13509-13513
Chiral catalysts tolerating photochemical reactions are in great demand for the vast development of visible‐light‐induced asymmetric synthesis. Now, chiral octahedral complexes based on earth‐abundant metal and chiral N4 ligands are reported. One well‐defined chiral CoII‐complex is shown to be an efficient catalyst in the visible‐light‐induced conjugated addition of enones by alkyl and acyl radicals, providing synthetically valued chiral ketones and 1,4‐dicarbonyls in 47–>99 % yields with up to 97:3 e.r. 相似文献
10.
Synthesis of β‐Substituted γ‐Aminobutyric Acid Derivatives through Enantioselective Photoredox Catalysis 下载免费PDF全文
Jiajia Ma Jiahui Lin Lifang Zhao Dr. Klaus Harms Michael Marsch Dr. Xiulan Xie Prof. Dr. Eric Meggers 《Angewandte Chemie (International ed. in English)》2018,57(35):11193-11197
β‐Substituted chiral γ‐aminobutyric acids feature important biological activities and are valuable intermediates for the synthesis of pharmaceuticals. Herein, an efficient catalytic enantioselective approach for the synthesis of β‐substituted γ‐aminobutyric acid derivatives through visible‐light‐induced photocatalyst‐free asymmetric radical conjugate additions is reported. Various β‐substituted γ‐aminobutyric acid analogues, including previously inaccessible derivatives containing fluorinated quaternary stereocenters, were obtained in good yields (42–89 %) and with excellent enantioselectivity (90–97 % ee). Synthetically valuable applications were demonstrated by providing straightforward synthetic access to the pharmaceuticals or related bioactive compounds (S)‐pregabalin, (R)‐baclofen, (R)‐rolipram, and (S)‐nebracetam. 相似文献
11.
Xiaohong Chen Yin Zhu Zhen Qiao Mingsheng Xie Lili Lin Dr. Xiaohua Liu Dr. Xiaoming Feng Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(33):10124-10129
An easily available and efficient chiral N,N′‐dioxide–nickel(II) complex catalyst has been developed for the direct catalytic asymmetric aldol reaction of α‐isothiocyanato imide with aldehydes which produces the products in morderate to high yields (up to 98 %) with excellent diastereo‐ (up to >99:1 d.r.) and enantioselectivities (up to >99 % ee). A variety of aromatic, heteroaromatic, α,β‐unsaturated, and aliphatic aldehydes were found to be suitable substrates in the presence of 2.5 mol % L ‐proline‐derived N,N′‐dioxide L5 –nickel(II) complex. This process was air‐tolerant and easily manipulated with available reagents. Based on experimental investigations, a possible transition state has been proposed to explain the origin of reactivity and asymmetric inductivity. 相似文献
12.
Enantio‐ and Diastereoselective Cyclopropanation of 1‐Alkenylboronates: Synthesis of 1‐Boryl‐2,3‐Disubstituted Cyclopropanes 下载免费PDF全文
Dr. Javier Carreras Dr. Ana Caballero Prof. Dr. Pedro J. Pérez 《Angewandte Chemie (International ed. in English)》2018,57(9):2334-2338
A novel, highly enantio‐ and diastereoselective synthesis of 1‐boryl‐2,3‐disubstituted cyclopropanes has been developed by means of the cyclopropanation of alkenylboronates with ethyl diazoacetate in the presence of catalytic amounts of a chiral copper(I) complex. The products can also be directly accessed from alkynes through an operationally simple, sequential hydroboration–cyclopropanation protocol. The resulting enantioenriched 1‐boryl‐2,3‐disubstituted cyclopropanes are versatile synthetic intermediates that undergo further transformations at the carbon–boron bond. 相似文献
13.
Pablo Bonilla Dr. Yannick P. Rey Dr. Catherine M. Holden Prof. Dr. Paolo Melchiorre 《Angewandte Chemie (International ed. in English)》2018,57(39):12819-12823
Radical cascade processes are invaluable for their ability to rapidly construct complex chiral molecules from simple substrates. However, implementing catalytic asymmetric variants is difficult. Reported herein is a visible‐light‐mediated organocatalytic strategy that exploits the excited‐state reactivity of chiral iminium ions to trigger radical cascade reactions with high enantioselectivity. By combining two sequential radical‐based bond‐forming events, the method converts unactivated olefins and α,β‐unsaturated aldehydes into chiral adducts in a single step. The implementation of an asymmetric three‐component radical cascade further demonstrates the complexity‐generating power of this photochemical strategy. 相似文献
14.
Nickel(II)‐Catalyzed Asymmetric Propargyl and Allyl Claisen Rearrangements to Allenyl‐ and Allyl‐Substituted β‐Ketoesters 下载免费PDF全文
Yangbin Liu Haipeng Hu Haifeng Zheng Yong Xia Prof. Dr. Xiaohua Liu Dr. Lili Lin Prof. Dr. Xiaoming Feng 《Angewandte Chemie (International ed. in English)》2014,53(43):11579-11582
Highly efficient catalytic asymmetric Claisen rearrangements of O‐propargyl β‐ketoesters and O‐allyl β‐ketoesters have been accomplished under mild reaction conditions. In the presence of the chiral N,N′‐dioxide/NiII complex, a wide range of allenyl/allyl‐substituted all‐carbon quaternary β‐ketoesters was obtained in generally good yield (up to 99 %) and high diastereoselectivity (up to 99:1 d.r.) with excellent enantioselectivity (up to 99 % ee). 相似文献
15.
Enantioselective Visible‐Light‐Induced Radical‐Addition Reactions to 3‐Alkylidene Indolin‐2‐ones 下载免费PDF全文
Dr. Dominik Lenhart Dr. Andreas Bauer Dr. Alexander Pöthig Prof. Dr. Thorsten Bach 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(19):6519-6523
The title compounds underwent a facile and high‐yielding addition reaction (19 examples, 66–99 % yield) with various N‐(trimethylsilyl)methyl‐substituted amines upon irradiation with visible light and catalysis by a metal complex. If the alkylidene substituent is non‐symmetric and if the reaction is performed in the presence of a chiral hydrogen‐bonding template, products are obtained with significant enantioselectivity (58–72 % ee) as a mixture of diastereoisomers. Mechanistic studies suggest a closed catalytic cycle for the photoactive metal complex. However, the silyl transfer from the amine occurs not only to the product, but also to the substrate, and interferes with the desired chirality transfer. 相似文献
16.
Aromatic Amide‐Derived Non‐Biaryl Atropisomers as Highly Efficient Ligands in Silver‐Catalyzed Asymmetric Cycloaddition Reactions 下载免费PDF全文
Xing‐Feng Bai Tao Song Dr. Zheng Xu Prof. Chun‐Gu Xia Wei‐Sheng Huang Prof. Dr. Li‐Wen Xu 《Angewandte Chemie (International ed. in English)》2015,54(17):5255-5259
The synthesis of a series of aromatic amide‐derived non‐biaryl atropisomers with a phosphine group and multiple stereogenic centers is reported. The novel phosphine ligands exhibit high diastereo‐ and enantioselectivities (up to >99:1 d.r., 95–99 % ee) as well as yields in the silver‐catalyzed asymmetric [3+2] cycloaddition of aldiminoesters with nitroalkenes, which provides a highly enantioselective strategy for the synthesis of optically pure nitro‐substituted pyrrolidines. In addition, the experimental results with regard to the carbon stereogenic center as well as the amide stereochemistry confirmed the potential of hemilabile atropisomers as chiral ligand in catalytic asymmetric [3+2] cycloaddition reaction. 相似文献
17.
Haiyan Zhang Wei Huang Tongtong Wang Fanke Meng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(32):11165-11169
Catalytic diastereo‐ and enantioselective hydroalkenylation of 3,3‐disubstituted cyclopropenes with readily accessible alkenylboronic acids, promoted by a chiral phosphine/Co complex, is presented. Such a process constitutes the unprecedented and direct introduction of a wide range of alkenyl groups onto the cyclopropane motif to afford multisubstituted cyclopropanes in up to 95 % yield with greater than 95:5 d.r. and 99:1 e.r. Functionalization of the products delivered enantioenriched cyclopropanes that are otherwise difficult to access. 相似文献
18.
Gram‐Scale Synthesis of Chiral Cyclopropane‐Containing Drugs and Drug Precursors with Engineered Myoglobin Catalysts Featuring Complementary Stereoselectivity 下载免费PDF全文
Dr. Priyanka Bajaj Dr. Gopeekrishnan Sreenilayam Dr. Vikas Tyagi Prof. Dr. Rudi Fasan 《Angewandte Chemie (International ed. in English)》2016,55(52):16110-16114
Engineered hemoproteins have recently emerged as promising systems for promoting asymmetric cyclopropanations, but variants featuring predictable, complementary stereoselectivity in these reactions have remained elusive. In this study, a rationally driven strategy was implemented and applied to engineer myoglobin variants capable of providing access to 1‐carboxy‐2‐aryl‐cyclopropanes with high trans‐(1R,2R) selectivity and catalytic activity. The stereoselectivity of these cyclopropanation biocatalysts complements that of trans‐(1S,2S)‐selective variants developed here and previously. In combination with whole‐cell biotransformations, these stereocomplementary biocatalysts enabled the multigram synthesis of the chiral cyclopropane core of four drugs (Tranylcypromine, Tasimelteon, Ticagrelor, and a TRPV1 inhibitor) in high yield and with excellent diastereo‐ and enantioselectivity (98–99.9% de; 96–99.9% ee). These biocatalytic strategies outperform currently available methods to produce these drugs. 相似文献
19.
Lei Shi Xingwang Wang Dr. Christian A. Sandoval Prof. Dr. Zheng Wang Prof. Dr. Hongji Li Jiang Wu Liting Yu Kuiling Ding Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(38):9855-9867
Well‐designed, self‐assembled, metal–organic frameworks were constructed by simple mixing of multitopic MonoPhos‐based ligands ( 3 ; MonoPhos=chiral, monodentate phosphoramidites based on the 1,1′‐bi‐2‐naphthol platform) and [Rh(cod)2]BF4 (cod=cycloocta‐1,5‐diene). This self‐supporting strategy allowed for simple and efficient catalyst immobilization without the use of extra added support, giving well‐characterized, insoluble (in toluene) polymeric materials ( 4 ). The resulting self‐supported catalysts ( 4 ) showed outstanding catalytic performance for the asymmetric hydrogenation of a number of α‐dehydroamino acids ( 5 ) and 2‐aryl enamides ( 7 ) with enantiomeric excess (ee) ranges of 94–98 % and 90–98 %, respectively. The linker moiety in 4 influenced the reactivity significantly, albeit with slight impact on the enantioselectivity. Acquisition of reaction profiles under steady‐state conditions showed 4 h and 4 i to have the highest reactivity (turnover frequency (TOF)=95 and 97 h?1 at 2 atm, respectively), whereas appropriate substrate/catalyst matching was needed for optimum chiral induction. The former was recycled 10 times without loss in ee (95–96 %), although a drop in TOF of approximately 20 % per cycle was observed. The estimation of effective catalytic sites in self‐supported catalyst 4 e was also carried out by isolation and hydrogenation of catalyst–substrate complex, showing about 37 % of the RhI centers in the self‐supported catalyst 4 e are accessible to substrate 5 c in the catalysis. A continuous flow reaction system using an activated C/ 4 h mixture as stationary‐phase catalyst for the asymmetric hydrogenation of 5 b was developed and run continuously for a total of 144 h with >99 % conversion and 96–97 % enantioselectivity. The total Rh leaching in the product solution is 1.7 % of that in original catalyst 4 h . 相似文献
20.
Asymmetric Michael Addition/Intramolecular Cyclization Catalyzed by Bifunctional Tertiary Amine–Squaramides: Construction of Chiral 2‐Amino‐4H‐chromene‐3‐Carbonitrile Derivatives 下载免费PDF全文
The efficient asymmetric Michael addition/intramolecular cyclization of malononitrile with dienones catalyzed by a chiral bifunctional tertiary amine–squaramide catalyst for the synthesis of chiral 2‐amino‐4H‐chromene‐3‐carbonitrile derivatives was developed. The corresponding products were obtained in good to excellent yields (up to 99 %) with excellent enantioselectivities (up to 98 % ee) for most of the bisarylidenecyclopentanones. 相似文献