- Novel cobalt(0)- or magnesium-mediated approaches to β-ketophosphonates
-
Two novel approaches to β-ketophosphonates, based on cobalt(0)- or magnesium-mediated reactions of α-halophosphonates with esters are described.
- Orsini, Fulvia,Di Teodoro, Emanuela,Ferrari, Marinella
-
-
Read Online
- Construction of Dual-Active-Site Copper Catalyst Containing both Cu-N3 and Cu-N4 Sites
-
Clear recognition and rational construction of suitable active center for specific reaction is always of great significance in designing highly efficient catalysts. Herein, a dual-active-site copper catalyst (DAS-Cu) containing both Cu-N3 and Cu-N4 sites is reported. Such catalysts show extremely high catalytic performance (yield: up to 97%) toward oxyphosphorylation of alkenes, while catalysts with single active site (Cu-N3 or Cu-N4) are chemically inert in this reaction. Combined with theoretical and experimental results, the different roles of two different Cu active sites in this reaction are further identified. Cu-N3 site captures the oxygen and trigger further oxidizing process, while Cu-N4 site provides moderate adsorption sites for the protection of phosphonyl radicals. This work deeply discloses the significant cooperated role with two single-atomic sites in one catalytic active center and brings up a valuable clue for the rational design of better-performing heterogeneous catalyst.
- Xiong, Yu,Wang, Shibin,Chen, Wenxing,Zhang, Jian,Li, Qiheng,Hu, Han-Shi,Zheng, Lirong,Yan, Wensheng,Gu, Lin,Wang, Dingsheng,Li, Yadong
-
-
Read Online
- Synthesis and antiproliferative evaluation of new zampanolide mimics
-
(?)-Zampanolide is a marine microtubule-stabilizing macrolide that has been shown by in vitro experiments to be a promising anticancer lead compound. Through its unique covalent-binding with β-tubulin, zampanolide exhibits cytotoxic potency towards multi-drug resistant cancer cells that is superior to paclitaxel. However, the limited availability of zampanolide impedes its further in vivo evaluation as a viable drug candidate. Zampanolide is envisioned to become more drug-like if its chemically fragile side chain can be stabilized; hence, this project aims to develop mimics of zampanolide with a stable side chain using straightforward synthetic methods. To this end, twelve novel zampanolide mimics (51-62) with conjugated and planar side chains have been synthesized via a 24-step sequence for each mimic from commercially available 2-butyn-1-ol as starting material. A Horner-Wadsworth-Emmons reaction incorporates the α,β-unsaturated ketone side chain and also closes the core macrocycle. WST-1 cell proliferation assays in three docetaxel-sensitive and two docetaxel-resistant human prostate cancer cell models confirm that a suitably designed side chain can serve as a bioisostere for the N-acyl hemiaminal side chain in zampanolide. Mimic 52 with a 17R chiral center was identified as the optimal candidate with IC50 values of 0.29-0.46 μM against both docetaxel-sensitive (PC-3 and DU145) and docetaxel-resistant prostate cancer cell lines (PC-3/DTX and DU145/DTX). Zampanolide mimic 52 exhibited equivalent antiproliferative potency towards both docetaxel-sensitive and docetaxel-resistant cell lines, with relative resistance in the range of 0.9-1.6.
- Chen, Guanglin,Patanapongpibul, Manee,Jiang, Ziran,Zhang, Qiang,Zheng, Shilong,Wang, Guangdi,White, James D.,Chen, Qiao-Hong
-
-
Read Online
- Synthesis of 2-oxophosphorindolines: Via the copper-catalyzed intramolecular aromatic C-H insertion of diazophosphonamidates
-
An efficient synthetic method for 2-ethoxy-2-oxophosphorindolines, benzo-γ-phospholactams, has been successfully achieved through the copper-catalyzed intramolecular aromatic C-H insertion of diazophosphonamidates with up to 97% yield. The current method has advantages of mild and clean conditions, and an inexpensive catalyst.
- Huang, Peipei,Xu, Jiaxi
-
-
Read Online
- Direct and straightforward transfer of C1 functionalized synthons to phosphorous electrophiles for accessinggem-P-containing methanes
-
The direct transfer of different α-substituted methyllithium reagents to chlorinated phosphorous electrophiles of diverse oxidation state (phosphates, phosphine oxides and phosphines) is proposed as an effective strategy to synthesize geminal P-containing
- Touqeer, Saad,Ielo, Laura,Miele, Margherita,Urban, Ernst,Holzer, Wolfgang,Pace, Vittorio
-
supporting information
p. 2425 - 2429
(2021/04/02)
-
- Copper-Catalyzed Microwave-Expedited Oxyphosphorylation of Alkynes with Diethyl Phosphite and t-Butyl Hydroperoxide Synthesis of Densely Functionalized Phosphonylated Indenones
-
Treatment of alkynes with diethyl phosphite and t-butyl hydroperoxide in the presence of [Cu(MeCN)4]BF4 under microwave irradiation produced the oxyphosphorylation of the triple bond, giving rise to the corresponding β-ketophosphonates in moderate-to-good yields. When the triple bond was conjugated to a carbonyl group bearing an aromatic ring, it led to the cyclization of the resulting ketone intermediate, producing eventually different phosphonylated indenones.
- Maciás-Benítez, Pablo,Sierra-Padilla, Alfonso,Tenorio, Manuel J.,Moreno-Dorado, F. Javier,Guerra, Francisco M.
-
p. 16409 - 16424
(2021/11/16)
-
- Iron-Catalyzed and Air-Mediated C(sp3)?H Phosphorylation of 1,3-Dicarbonyl Compounds Involving C?C Bond Cleavage
-
A C(sp3)?H phosphorylation has been achieved via the iron-catalyzed cross-coupling reactions between 1,3-dicarbonyl compounds and P(O)?H compounds involving C?C bond cleavages with air as the oxidant. This transformation provides a straightforward way to construct C(sp3)?P bonds, leading to the formation of β-ketophosphine oxides in up to 93% yield with good functional group tolerance. (Figure presented.).
- Ou, Yingcong,Huang, Yuanting,Liu, Yu,Huo, Yanping,Gao, Yang,Li, Xianwei,Chen, Qian
-
supporting information
p. 5783 - 5787
(2020/11/30)
-
- Copper ferrite nanoparticles catalyzed formation of β-Ketophosphonates via oxyphosphorylation of styrenes with H-phosphonates: A DFT study on UV–vis absorption spectra
-
Typical copper ferrite nanoparticles (CuFe2O4) were used as a catalyst for one-pot synthesis of β-ketophosphonates via the reaction of alkenes with H-phosphonates under conventional heating conditions. The catalyst was prepared by using the coprecipitation method and was analyzed by physiochemical techniques. By using this catalyst system, several types of useful and new β-ketophosphonate products were obtained in very good to excellent yields under optimized reaction conditions in a novel way. Furthermore, the catalyst is recyclable and reusable from the reaction.
- Azaryan, Reza,Daneshfar, Maryam,Moghaddam, Firouz Matloubi,Pirat, Jean-Luc
-
-
- Access to chiral α-substituted-β-hydroxy arylphosphonates enabled by biocatalytic dynamic reductive kinetic resolution
-
Ketoreductase (KRED)-catalyzed dynamic reductive kinetic resolution (DYRKR) of α-substituted-β-keto arylphosphonates was developed as a generic and stereoselective approach to synthesize chiral α-substituted-β-hydroxy arylphosphonates, with moderate-to-excellent isolated yield (up to 96%), good-to-excellent diastereoselectivity (up to >99 : 99% ee) being achieved.
- Chen, Fener,Huang, Zedu,Li, Zihan,Tao, Yuan,Wang, Zexu,Wu, Xiaofan,Yu, Xiaomin,Zeng, Yiping
-
supporting information
p. 2672 - 2677
(2020/04/17)
-
- Bivalent copper complex containing diphosphine ortho-position carborane ligand, preparation method and application thereof
-
The invention relates to a bivalent copper complex containing a diphosphine ortho-position carborane ligand, a preparation method and application thereof. The copper complex is prepared by the following method of: adding an n-BuLi solution dropwise into an ortho-position carborane o-C2B10H12 solution, and carrying out stirring reaction, then adding halogenated phosphine for continuous reaction, adding copper acetate Cu(OAc)2 into the reaction system for continuous reaction, after the reaction is finished, performing separating to obtain the diphosphine ortho-position carborane ligand, and applying the copper complex to catalytic synthesis of a beta-carbonyl phosphine oxide compound. Compared with the prior art, the synthesis process has excellent selectivity and high yield, the copper complex can catalyze alpha-haloketone and phosphite to react to synthesize the beta-carbonyl phosphine oxide compound under the room temperature condition, and the reaction is efficient, green and environmentally friendly.
- -
-
Paragraph 0029; 0033-0036
(2020/09/16)
-
- An efficient preparation of β-ketophosphine oxides from alkynylphosphine oxides with benzaldehyde oxime as a hydroxide source
-
An effective and facile transitio-metal-free method has been developed for the synthesis of β-ketophosphine oxides from alkynylphosphine oxides with benzaldehyde oxime as a hydroxide surrogate. The current methodology provides simple access to various β-ketophosphine oxides in moderate to excellent yields with a broad substrate scope.
- Chen, Lu-Lu,Zhang, Jing-Wen,Yang, Wan-Wan,Chen, Pei,Chen, Dan-Yun,Wang, Yan-Bo
-
p. 3003 - 3009
(2019/03/20)
-
- General [4 + 1] Cyclization Approach to Access 2,2-Disubstituted Tetrahydrofurans Enabled by Electrophilic Bifunctional Peroxides
-
A general [4 + 1] cyclization reaction of carbonyl nucleophiles with 2-iodomethylallyl peroxides, which function as unique electrophilic oxygen synthons, for the synthesis of a broad range of 2,2-disubstituted tetrahydrofurans is achieved under operationally simple conditions. The unprecedented asymmetric version of such reaction is also realized via chiral auxiliary-assisted cyclization, thus providing a distinct approach to access chiral tetrahydrofurans with high diastereoselectivities. The new method can be applied to the synthesis of core structure of posaconazole drug.
- Gao, Min,Zhao, Yukun,Zhong, Chen,Liu, Shengshu,Liu, Pengkang,Yin, Qi,Hu, Lin
-
supporting information
p. 5679 - 5684
(2019/08/01)
-
- Mukaiyama reagent-promoted metal-free preparation of alkynyl sulfones and phosphonates under mild conditions
-
An efficient and mild route for the formation sulfur or phosphor-substituted alkynes was herein demonstrated. The Mukaiyama reagent-mediated transformation started from easily-accessible substrates without carbon-carbon triple bonds, and the reaction proceeded under mild conditions (room temperature) in a one-pot manner, requiring for no transition metal-catalysts. The practical protocol featured for good functional groups tolerance (up to 41 examples) and high efficiency (up to 91% yields) towards alkynyl sulfones and alkynyl phosphonates at low cost.
- Qi, Danyang,Dong, Wanrong,Peng, Zhihong,Zhang, Yingjun,An
-
-
- Direct synthesis of alkynylphosphonates from alkynes and phosphite esters catalyzed by Cu/Cu2O nanoparticles supported on Nb2O5
-
The aerobic oxidative coupling of alkynes and phosphite esters can be catalyzed by Cu/Cu2O nanoparticles supported on Nb2O5 (Cu/Cu2O@Nb2O5) to efficiently afford alkynylphosphonates. The catalyst can be reused by filtration and reduction. According to the results of control experiments and characterization data, the supporter Nb2O5 can reduce the electronic density of Cu and absorb the phosphite esters due to its strong Lewis acid sites, which may enhance the reaction efficiently.
- Yuan, Tao,Chen, Fei,Lu, Guo-ping
-
p. 13957 - 13962
(2018/08/21)
-
- Base-Promoted Direct Oxyphosphorylation of Alkynes with H-Phosphine Oxides in the Presence of Water
-
We have developed a simple method for the oxyphosphorylation of arylalkynes to give β-keto phosphine oxides without the assistance of any transition metal. An inorganic base promoted the oxyphosphorylation and water played a synergistic role in the formation of various β-keto phosphine oxides. The reaction showed a wide structural scope and broad functional-group tolerance, and it proceeded under mild reaction conditions. This method solved the problem of metal dependence in the oxyphosphorylation of alkynes, providing a potential application in organic chemistry. Control experiments revealed the mechanism of the oxyphosphorylation and the synergistic role played by water in the radical process.
- Zhong, Wenwu,Tan, Tao,Shi, Lei,Zeng, Xue
-
p. 1379 - 1384
(2018/04/24)
-
- Novel synthesis method for phosphate compounds
-
The invention discloses a novel synthesis method for phosphate compounds. Specifically, the method comprises steps as follows: alcohol with the structure (I), H-phosphite with the structure (II), bivalent cobalt salt and n-hydroxyphthalimide are dispersed in a solvent sequentially, oxygen is introduced into a mixture, heating and stirring are performed, and the phosphate compounds with a structure (III) shown in the description can be obtained. The novel method for efficiently synthesizing the phosphate target compounds from cheap and available alcohol and H-phosphite compounds as starting materials for the reaction, bivalent cobalt salt and n-hydroxyphthalimide as co-catalysts as well as oxygen as an oxidizing agent through aerobic oxidative coupling is provided for the first time. The method has the advantages that reaction conditions are mild, operation is simple, the raw materials are cheap and available, product structures are diversified, the yield is high and the like, and great application value and broad industrial prospect are shown.
- -
-
Paragraph 0034; 0035; 0036; 0037; 0038; 0039
(2018/01/19)
-
- Mn(OAc)3-Promoted Oxidative Csp3-P Bond Formation through Csp2-Csp2 and P-H Bond Cleavage: Access to β-Ketophosphonates
-
The Mn(OAc)3-promoted oxidative phosphonylation of N,N-dimethylenaminones with H-phosphonates, involving a chemo- and regioselective Csp2-Csp2 bond cleavage and Csp3-P bond formation in one step, provided successfully functionalized β-ketophosphonates under mild reaction conditions. Oxidative Csp3-H/P-H cross-coupling reactions via Csp3-C(C=O) bond cleavage and mechanistic studies are conducted preliminarily, and a possible mechanism is proposed. This novel method proceeds in good to excellent yields, shows operational simplicity, broad substrate scope, and large-scale preparation.
- Zhou, Pan,Hu, Biao,Li, Lingdan,Rao, Kairui,Yang, Jiao,Yu, Fuchao
-
p. 13268 - 13276
(2017/12/26)
-
- Copper-Catalyzed Direct Oxyphosphorylation of Enamides with P(O)-H Compounds and Dioxygen
-
A simple and convenient copper-catalyzed direct oxyphosphorylation of enamides with P(O)-H compounds and dioxygen has been developed under mild conditions. This methodology can allow the synthesis of a series of valuable β-ketophosphine oxides/β-ketophosphonates in moderate to good yields with a broad substrate scope simply by using readily-available starting materials.
- Liang, Wu,Zhang, Zhijie,Yi, Dong,Fu, Qiang,Chen, Suyuan,Yang, Lu,Du, Fengtian,Ji, Jianxin,Wei, Wei
-
supporting information
p. 1378 - 138
(2017/10/06)
-
- Silver-Catalyzed Oxidative C(sp3)?P Bond Formation through C?C and P?H Bond Cleavage
-
The silver-catalyzed oxidative C(sp3)?H/P?H cross-coupling of 1,3-dicarbonyl compounds with H-phosphonates, followed by a chemo- and regioselective C(sp3)?C(CO) bond-cleavage step, provided heavily functionalized β-ketophosphonates. This novel method based on a readily available reaction system exhibits wide scope, high functional-group tolerance, and exclusive selectivity.
- Li, Lili,Huang, Wenbin,Chen, Lijin,Dong, Jiaxing,Ma, Xuebing,Peng, Yungui
-
supporting information
p. 10539 - 10544
(2017/08/22)
-
- Cu(i)/Fe(III)-Catalyzed C-P cross-coupling of styrenes with H-phosphine oxides: A facile and selective synthesis of alkenylphosphine oxides and β-ketophosphonates
-
Cu(i)/Fe(iii)-Catalyzed phosphorylation and oxyphosphorylation of styrenes with H-phosphonates which can be controlled by varying the reaction temperature are developed. This study offers a new and expedient strategy for the synthesis of useful alkenylphosphine oxides and β-ketophosphonates in satisfactory yields. Moreover, the transformation is proposed to proceed via a radical process and exhibits a broad substrate scope and good functional group tolerance.
- Gu, Jian,Cai, Chun
-
supporting information
p. 4226 - 4230
(2017/07/10)
-
- MnIII-catalyzed phosphorylation of vinyl azides: The synthesis of β-keto phosphine oxides
-
MnIII-catalyzed functionalization of vinyl azides via phosphorylation was developed to synthesize various β-keto phosphine oxides in high yields. The transformation is operated in mild conditions and tolerant of a range of functional groups. Control reaction indicates that the reaction mechanism might proceed via the generation of a phosphonated iminyl radical intermediate.
- Tang, Pai,Zhang, Can,Chen, En,Chen, Binhui,Chen, Wenteng,Yu, Yongping
-
supporting information
p. 2157 - 2161
(2017/05/09)
-
- Acetonitrile-dependent oxyphosphorylation: A mild one-pot synthesis of β-ketophosphonates from alkenyl acids or alkenes
-
An efficient one-pot synthesis of β-ketophosphonates has been developed, via the reaction of α,β-alkenyl carboxylic acids or alkenes with H-phosphonates and air oxygen, catalyzed by CuSO4·5H2O in CH3CN. CH3CN plays a decisive role, probably by forming an active oxygen complex [(MeCN)nCuII-O-O·].
- Chen, Xi,Chen, Xiaolan,Li, Xu,Qu, Chen,Qu, Lingbo,Bi, Wenzhu,Sun, Kai,Zhao, Yufen
-
p. 2439 - 2446
(2017/04/03)
-
- A process for preparing β - carbonyl phosphine ester method
-
The invention discloses a method for synthesizing beta-carboxyl phosphate from alkyne or alkynyl carboxylic compounds and phosphite ester in the presence of copper/iron salt serving as catalysts and molecular oxygen serving as an oxidant. According to the method, multifunctional beta-carboxyl phosphate is obtained by virtue of a novel method having wide substrate range in the presence of the inexpensive catalysts (copper salts and iron salts) in oxygen, which is in a sharp contrast with previously reported view that alkyne cannot act in the presence of molecular oxygen. The method disclosed by the invention has the advantages of mild reaction conditions, easily available raw materials, good compatibility with various reactants, strong practicality and high yield and can be widely applied to various functional reactions.
- -
-
Paragraph 0078; 0079; 0080; 0081; 0082
(2017/07/31)
-
- Preparation method for synthesizing beta-carbonyl phosphonate derivatives via olefin
-
The invention discloses a method for synthesizing beta-carbonyl phosphonate derivatives via olefin and belongs to the field of organic chemistry. In the method, olefin (or olefin acid) and H-phosphite are used as raw materials, CuSO4.5H2O is used as a catalyst, and beta-carbonyl phosphonate derivatives are synthesized by heating reaction. The method is cheap and readily available in raw materials, simple in operation, mild in reaction condition and high in synthetic yield, and is suitable for industrialized production. The derivatives are often used as intermediates for synthesizing alpha, beta-unsaturated carbonyl compounds, and the derivatives also have wide bioactivity and significant metal compounding capability and play an irreplaceable role in medicinal chemistry, biological chemistry and inorganic chemistry.
- -
-
Paragraph 0016; 0017; 0018
(2017/08/25)
-
- Mn(OAc)3-Mediated Synthesis of 3-Phosphonyldihydrofurans from β-Ketophosphonates and Alkenes
-
A new, general method for the synthesis of 3-phosphonyldihydrofuran derivatives has been achieved through Mn(OAc)3-mediated radical cyclization between β-ketophosphonates and alkenes. This transformation allows the direct formation of C-C/C-O bonds and the construction of a dihydrofuran ring in one reaction with operational simplicity and excellent functional-group compatibility.
- Lu, Guozhang,Lin, Binzhou,Gao, Yuzhen,Ying, Jianxi,Tang, Guo,Zhao, Yufen
-
p. 724 - 728
(2017/03/21)
-
- Beta-carboxyl phosphate compounds and preparation method thereof
-
The invention discloses beta-carboxyl phosphate compounds. The compounds specifically have the structural formula shown in the specification, wherein R1 is aryl or substituted aryl; R2 is alkyl. Olefin and H-phosphite are taken as raw materials, and a silver-catalyzing radical mechanism is firstly used for synthesis of the beta-carboxyl phosphate compounds. No alkaline additives are required to be added, the reaction conditions are mild, and large-scale production is easy to realize. Experimental results prove that the yield of the obtained beta-carboxyl phosphate compounds can be up to 70%.
- -
-
Paragraph 0047; 0048; 0050; 0051; 0053; 0054
(2017/08/28)
-
- Preparation method of beta-ketone substituted phosphate ester compound
-
The invention provides a preparation method of a beta-ketone substituted phosphate ester compound. The beta-ketone substituted phosphate ester compound is generated through a reaction of initial materials comprising alkenyl azide and phosphite ester in an organic solvent with manganese acetate as an oxidant. The preparation method has the advantages of reasonable design, easily available raw materials, mild reaction conditions, no high temperature reflow, high safety and convenience, and high yield, and allows the yield of most of products to be 70% or above. The preparation method is a method for constructing the beta-ketone substituted phosphate ester compound and having the advantages of simple operation, fastness, mildness and diversification; and the two initial raw materials are obtained through a one-step technology, so reaction raw materials are cheap and can be easily obtained. The general formula (I) of the beta-ketone substituted phosphate ester compound is shown in the description.
- -
-
Paragraph 0032-0036
(2019/08/28)
-
- Substituent-Controlled Chemoselective Cleavage of C = C or Csp2 - C(CO) Bond in α,β-Unsaturated Carbonyl Compounds with H-Phosphonates Leading to β-Ketophosphonates
-
An unprecedented substituent-controlled chemoselective cleavage of C = C double bond or C(sp2)-C(CO) bond along with aerobic phosphorylation of α,β-unsaturated carbonyl compounds with H-phosphonates through a radical process has been disclosed. The current strategy provides an access to β-ketophosphonates under mild conditions with a wide substrate scope.
- Zhou, Yao,Rao, Changqing,Mai, Shaoyu,Song, Qiuling
-
p. 2027 - 2034
(2016/03/15)
-
- Synthesis of α-trifluoromethyl-β-keto phosphonates by electrophilic trifluoromethylation with Togni reagent
-
A new synthetic method of trifluoromethylated phosphonates was developed via electrophilic trifluoromethylation with Togni reagent. A variety of β-keto phosphonates were converted into the corresponding α-trifluoromethyl-β-keto phosphonates in moderate to good yields. This protocol could also be extended to other fluoroalkylation reactions, such as pentafluoroethylation.
- Fu, Wen-Zhi,Huang, Yangen,Xu, Xiu-Hua,Qing, Feng-Ling
-
supporting information
p. 415 - 420
(2016/04/05)
-
- Β-carbonyl process for the preparation of phosphonic acid ester compound
-
The present invention discloses a preparation method for preparing beta-Ketophosphonates represented by a formula (III). The beta-Ketophosphonate is an oxygen-containing compound having a value, and is especially adopted as an important synthesis intermediate to be widely used in the famous HWE reaction to synthesize alpha,beta-unsaturated carbonyl compounds. According to the present invention, simple and commercialized olefin and hydrogen-phosphorite are adopted as raw materials to directly utilize oxygen as an oxidizing agent and an oxygen source under transition metal catalysis to prepare the beta-Ketophosphonates; the preparation method has advantages of cheap and easily available raw materials, mild reaction conditions, environmental-friendliness, high atom economy, wide substrate adaptability range, and no requirement of harsh reaction conditions such as equivalent organic metal reagent use, low temperature, no water, no oxygen and the like; and the method further has advantages of short preparation period, easy product purification, stable process conditions, convenient operation and safety, and is suitable for large-scale production.
- -
-
Paragraph 0057-0059
(2016/12/01)
-
- Addressing the Glycine-Rich Loop of Protein Kinases by a Multi-Facetted Interaction Network: Inhibition of PKA and a PKB Mimic
-
Protein kinases continue to be hot targets in drug discovery research, as they are involved in many essential cellular processes and their deregulation can lead to a variety of diseases. A series of 32 enantiomerically pure inhibitors was synthesized and tested towards protein kinase A (PKA) and protein kinase B mimic PKAB3 (PKA triple mutant). The ligands bind to the hinge region, ribose pocket, and glycine-rich loop at the ATP site. Biological assays showed high potency against PKA, with Ki values in the low nanomolar range. The investigation demonstrates the significance of targeting the often neglected glycine-rich loop for gaining high binding potency. X-ray co-crystal structures revealed a multi-facetted network of ligand-loop interactions for the tightest binders, involving orthogonal dipolar contacts, sulfur and other dispersive contacts, amide-π stacking, and H-bonding to organofluorine, besides efficient water replacement. The network was analyzed in a computational approach.
- Lauber, Birgit S.,Hardegger, Leo A.,Asraful, Alam K.,Lund, Bjarte A.,Dumele, Oliver,Harder, Michael,Kuhn, Bernd,Engh, Richard A.,Diederich, Fran?ois
-
supporting information
p. 211 - 221
(2016/01/25)
-
- Palladium-Catalyzed Long-Range Deconjugative Isomerization of Highly Substituted α,β-Unsaturated Carbonyl Compounds
-
The long-range deconjugative isomerization of a broad range of α,β-unsaturated amides, esters, and ketones by an in situ generated palladium hydride catalyst is described. This redox-economical process is triggered by a hydrometalation event and is thermodynamically driven by the refunctionalization of a primary or a secondary alcohol into an aldehyde or a ketone. Di-, tri-, and tetrasubstituted carbon-carbon double bonds react with similar efficiency; the system is tolerant toward a variety of functional groups, and olefin migration can be sustained over 30 carbon atoms. The refunctionalized products are usually isolated in good to excellent yield. Mechanistic investigations are in support of a chain-walking process consisting of repeated migratory insertions and β-H eliminations. The bidirectionality of the isomerization reaction was established by isotopic labeling experiments using a substrate with a double bond isolated from both terminal functions. The palladium hydride was also found to be directly involved in the product-forming tautomerization step. The ambiphilic character of the in situ generated [Pd-H] was demonstrated using isomeric trisubstituted α,β-unsaturated esters. Finally, the high levels of enantioselectivity obtained in the isomerization of a small set of α-substituted α,β-unsaturated ketones augur well for the successful development of an enantioselective version of this unconventional isomerization.
- Lin, Luqing,Romano, Ciro,Mazet, Clément
-
supporting information
p. 10344 - 10350
(2016/08/31)
-
- Palladium-Catalyzed Oxidative Cyclization for the Synthesis of Indolyl/Pyrrolyl 3-Phosphonates
-
Imino-/enaminophosphonates derived from amines and diethyl phenacyl phosphonates undergo oxidative cyclization via C H bond activation catalyzed by palladium chloride to provide a convenient route for the synthesis of substituted indol-3-yl and pyrrol-3-yl phosphonates. (Figure presented.) .
- Mishra, Aniket,Deb, Indubhusan
-
p. 2267 - 2272
(2016/07/29)
-
- Synthesis of β-ketophosphonates via AgNO3-catalyzed hydration of alkynylphosphonates: A rate-enhancement effect of methanol
-
β-Ketophosphonates were prepared via AgNO3-catalyzed hydration of alkynylphosphonates with a dramatic rate-enhancement effect of methanol. This benign aqueous-methanol method catalyzed by a low-cost catalyst has simple, atom-economical procedure, and was used effectively with a wide range of substrates.
- Xiang, Jiannan,Yi, Niannian,Wang, Ruijia,Lu, Linghui,Zou, Huaxu,Pan, Yuan,He, Weimin
-
p. 694 - 699
(2015/02/02)
-
- β-Ketophosphonates formation via deesterification or deamidation of cinnamyl/alkynyl carboxylates or amides with H-phosphonates
-
We report here an unprecedented Fe/Cu synergistically catalyzed deesterificative or deamidative oxyphosphorylation of unsaturated carboxylates or amides with H-phosphonates. The valuable β-ketophosphonates were obtained along with chemoselective cleavage of Csp2-C(CO) or Csp-C(CO) bonds in good yields under oxygen atmosphere with a wide substrate scope.
- Zhou, Yao,Zhou, Mingxin,Chen, Ming,Su, Jihu,Du, Jiangfeng,Song, Qiuling
-
p. 103977 - 103981
(2015/12/24)
-
- Base-induced one-pot preparation of N- or P-substituted alkynes
-
An efficient method for the formation of C(sp)-N or C(sp)-P bonds is described. The facile transformation proceeds under mild conditions (0 or -20 °C) in a one-pot manner, and does not require transition-metal catalysts. The base-induced protocol exhibits good functional group tolerance (up to 44 examples) and high efficiency (up to 94 % yield) towards rare heteroatom-substituted acetylenes (N or P). Furthermore, the proposed mechanism was supported by the isolation of a key intermediate. An efficient method for the formation of C(sp)-N or C(sp)-P bonds is described. The facile transformation proceeds in the absence of any transition-metal catalysts under mild conditions (0 or -20 °C) in a one-pot manner with good functional group compatibility and with high efficiency.
- Zhang, Yang,Zhang, Yanqin,Xiao, Jing,Peng, Zhihong,Dong, Wanrong,An, Delie
-
supporting information
p. 7806 - 7815
(2015/12/31)
-
- Direct synthesis of β-ketophosphonates and vinyl phosphonates from alkenes or alkynes catalyzed by CuNPs/ZnO
-
Copper nanoparticles (CuNPs) supported on ZnO have been shown to effectively catalyze the direct synthesis of β-ketophosphonates from alkenes or alkynes, and that of vinyl phosphonates from alkynes and diethylphosphite, under air and in the absence of any additive or ligand. When using alkynes as starting materials, the selectivity proved to be dependent on the nature of the alkyne. Thus, alkynes conjugated with an aromatic ring or a carbon-carbon double bond gave β-ketophosphonates as the main reaction products, whereas aliphatic alkynes or alkynes conjugated with a carbonyl group led to the formation of the corresponding vinyl phosphonates.
- Gutierrez, Victoria,Mascaró, Evangelina,Alonso, Francisco,Moglie, Yanina,Radivoy, Gabriel
-
p. 65739 - 65744
(2015/08/18)
-
- Cu/Fe-Cocatalyzed Formation of β-Ketophosphonates by a Domino Knoevenagel-Decarboxylation-Oxyphosphorylation Sequence from Aromatic Aldehydes and H-Phosphonates
-
A domino Knoevenagel-decarboxylation-alkene difunctionalization sequence has been developed for the conversion of benzaldehydes into β-ketophosphonates, catalyzed by a cooperative Cu/Fe system, whereby CP and CO bonds are formed simultaneously in a one-pot reaction. The reaction proceeds in good yields and with a broad substrate scope and environmentally benign conditions.
- Zhou, Mingxin,Zhou, Yao,Song, Qiuling
-
supporting information
p. 10654 - 10658
(2015/07/20)
-
- Copper/Iron-Catalyzed Aerobic Oxyphosphorylation of Terminal Alkynes Leading to β-Ketophosphonates
-
A copper/iron-catalyzed oxyphosphorylation of alkynes with H-phosphonates through a radical process was developed. The present protocol provides an attractive approach to β-ketophosphonates in moderate to good yields, with the advantages of readily available substrate, high functional group tolerance and operation simplicity. (Chemical Equation Presented).
- Yi, Niannian,Wang, Ruijia,Zou, Huaxu,He, Weibao,Fu, Wenqiang,He, Weimin
-
supporting information
p. 5023 - 5029
(2015/05/27)
-
- β-Ketophosphonate formation via aerobic oxyphosphorylation of alkynes or alkynyl carboxylic acids with H-phosphonates
-
A synergistic Cu/Fe-catalyzed aerobic oxyphosphorylation of alkynes or alkynyl carboxylic acids with H-phosphonate is disclosed. The useful β-ketophosphonate products were obtained in good yields under oxygen atmosphere in a novel way. This reaction exhibits a wide substrate scope, and the mechanistic experiments indicate that a radical mechanism forms both C-P and C=O bonds simultaneously. This mechanism contrasts existing aerobic difunctionalization of alkynes.
- Zhou, Mingxin,Chen, Ming,Zhou, Yao,Yang, Kai,Su, Jihu,Du, Jiangfeng,Song, Qiuling
-
p. 1786 - 1789
(2015/04/14)
-
- Copper-catalyzed tandem phosphination-decarboxylation-oxidation of alkynyl acids with H-phosphine oxides: A facile synthesis of β-ketophosphine oxides
-
The general method for the tandem phosphination-decarboxylation-oxidation of alkynyl acids under aerobic conditions has been developed. In the presence of CuSO4·5H2O and TBHP, the reactions provide a novel access to β-ketophosphine oxides in good to excellent yields. This transformation allows the direct formation of a P-C bond and the construction of a keto group in one reaction.
- Zhang, Pengbo,Zhang, Liangliang,Gao, Yuzhen,Xu, Jian,Fang, Hua,Tang, Guo,Zhao, Yufen
-
supporting information
p. 7839 - 7842
(2015/05/13)
-
- Silver-Catalyzed Aerobic Oxidative Decarboxylative Coupling of Arylpropiolic Acids with H-Phosphine Oxides: Mild and Facile Synthesis of β-Oxophosphine Oxides
-
A silver-catalyzed oxidative decarboxylative coupling reaction of arylpropiolic acids with H-phosphine oxides by using air as the terminal oxidant was developed. The reaction proceeds smoothly under mild conditions to give β-oxophosphine oxides in moderate to good yields. Preliminary mechanistic studies were conducted. Aerobic oxidative decarboxylative coupling of arylpropiolic acids with H-phosphine oxides is realized under silver catalysis. The reaction proceeds smoothly under mild conditions to give β-oxophosphine oxides in moderate to good yields. Preliminary mechanistic studies are conducted.
- Zeng, Yao-Fu,Tan, Dong-Hang,Lv, Wen-Xin,Li, Qingjiang,Wang, Honggen
-
supporting information
p. 4335 - 4338
(2015/07/27)
-
- A one-pot strategy to synthesize β-ketophosphonates: Silver/copper catalyzed direct oxyphosphorylation of alkynes with H-phosphonates and oxygen in the air
-
A highly efficient one-pot strategy has been developed for the synthesis of β-ketophosphonates directly from alkynes and dialkyl H-phosphonates in the presence of widely available AgNO3/CuSO4 and K2S2O8 at room temperature under open-air conditions.
- Chen, Xin,Li, Xu,Chen, Xiao-Lan,Qu, Ling-Bo,Chen, Jian-Yu,Sun, Kai,Liu, Zhi-Dong,Bi, Wen-Zhu,Xia, Ying-Ya,Wu, Hai-Tao,Zhao, Yu-Fen
-
supporting information
p. 3846 - 3849
(2015/03/30)
-
- Photocatalytic ?±-oxyamination of stable enolates, silyl enol ethers, and 2-oxoalkane phosphonic esters
-
Fast ?±-oxyamination of stable enolates, silyl enol ethers, and in situ deprotonated dialkyl 2-oxoalkane phosphonates and diphenyl-2-oxoalkyl phosphine oxides was performed in the presence of [Ru(bpy)3]2+ (bpy = 2,2a?2-bipyridyl) as a photocatalyst, 2,2,6,6-tetramethylpiperidine nitroxide (TEMPO), and visible light. The key step was the light-induced one-electron oxidation of TEMPO into the 2,2,6,6-tetramethylpiperidine- 1-oxoammonium ion, which was nucleophilically attacked to yield ?±-functionalized carbonyl compounds. The reaction time was significantly reduced by the use of the microreactor flow technique.
- Schroll, Peter,K??nig, Burkhard
-
supporting information
p. 309 - 313
(2015/03/03)
-
- Gold(I)-catalyzed hydration of alkynylphosphonates: Efficient access to β-ketophosphonates
-
A general, efficient, and highly regioselective protocol with the use of a gold(I) complex catalytic system for the transformation of alkynylphosphonates into the corresponding β-ketophosphonates has been successfully developed. This method produces a variety of β-ketophosphonates with the advantages of mild reaction conditions, high functional-group tolerance, and excellent yields. An efficient and mild gold-catalyzed hydration process for the regioselective synthesis of β-ketophosphonates directly from alkynylphosphonates is described. Twenty-two examples with yields of 85-97 % are reported. Different substituents including substituted aryl, alkyl, chloro, ester, sulfonoxyl, and phthalimide groups are tolerated; XPhos = 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl, Tf = trifluoromethylsulfonyl. Copyright
- Xie, Longyong,Yuan, Rui,Wang, Ruijia,Peng, Zhihong,Xiang, Jiannan,He, Weimin
-
supporting information
p. 2668 - 2671
(2014/05/06)
-
- Catalytic and direct methyl sulfonylation of alkenes and alkynes using a methyl sulfonyl radical generated from a DMSO, dioxygen and copper system
-
This paper describes an efficient method to β-keto methyl sulfones and (E)-vinyl methyl sulfones using DMSO as the substrate. The methyl sulfonyl radical generated from DMSO in the presence of catalytic Cu(i) under O2 atmosphere is believed to be involved in this reaction. Isotopic labeling and 18O2 experiments were performed to investigate the reaction mechanism.
- Jiang, Yaojia,Loh, Teck-Peng
-
p. 4939 - 4943
(2015/01/09)
-
- Synthetic entry into 1-phosphono-3-azabicyclo[3.1.0]hexanes
-
3-Azabicyclo[3.1.0]hex-2-en-1-yl phosphonates were prepared in a five-step reaction route from β-ketophosphonates. The key steps in this sequence are an atom-transfer radical cyclization and an unforeseen lithium-halogen exchange with n-BuLi. The cyclization reaction proceeds with excellent diastereoselectivity. The resulting cyclic imines were reduced, and 3-azabicyclo[3.1.0]hexan-1-yl phosphonates were obtained.
- Debrouwer, Wouter,Heugebaert, Thomas S. A.,Van Hecke, Kristof,Stevens, Christian V.
-
p. 8232 - 8241
(2013/09/24)
-
- Vinyl sulfone-based peptidomimetics as anti-trypanosomal agents: Design, synthesis, biological and computational evaluation
-
A series of vinyl sulfone-containing peptidomimetics were rationally designed, synthesized, and evaluated against Trypanosoma brucei brucei. These electrophilic compounds are likely to exert their antitrypanosomal activity via inhibition of trypanosomal cysteine proteases, TbCatB and rhodesain, through alkylation of a key cysteine residue within the protease active site. The series was designed to present complementary groups to naturally recognized peptide substrates while probing tolerance to a range of substitutions at the P1, P1′, and P2 positions. The most potent compound, 29 (EC50 = 70 nM, T. b. brucei whole cell assay), displayed minimal toxicity (>785 times selectivity) when assayed for cytotoxicity against the human promyelocytic leukemia (HL-60) cell line. Cells treated with compound 29, as with K777 (2), exhibited an increase in both the number of multinucleated cells and cells with swollen flagellar pockets. Computational analysis revealed a strong correlation between the hypothetical binding mode in TbCatB/rhodesain and trypanocidal activity in vitro.
- Dunny, Elizabeth,Doherty, William,Evans, Paul,Malthouse, J. Paul G.,Nolan, Derek,Knox, Andrew J.S.
-
supporting information
p. 6638 - 6650
(2013/10/01)
-
- Total synthesis of (-)-blepharocalyxin D and analogues
-
An efficient strategy for the total synthesis of (-)-blepharocalyxin D and an analogue is described. The key step involves an acid-mediated cascade process in which reaction of methyl 3,3-dimethoxypropanoate with γ,δ- unsaturated alcohols possessing diastereotopic styrenyl groups gives trans-fused bicyclic lactones with the creation of two rings and four stereocenters in one pot.
- Cons, Benjamin D.,Bunt, Adam J.,Bailey, Christopher D.,Willis, Christine L.
-
supporting information
p. 2046 - 2049
(2013/06/05)
-
- Palladium(II)-catalyzed hydration of alkynylphosphonates to β-ketophosphonates
-
A highly efficient palladium(II)-catalyzed hydration of a wide range of alkynylphosphonates to the corresponding β-ketophosphonates has been developed to give high yields at 80 °C in 1, 4-dioxane, with no acidic or alkaline cocatalysts required. The described catalytic system should provide an efficient alternative to highly toxic mercury-catalyzed methodologies and be useful in synthetic programs. Copyright
- Li, Xiubin,Hu, Gaobo,Luo, Ping,Tang, Guo,Gao, Yuxing,Xu, Pengxiang,Zhao, Yufen
-
supporting information
p. 2427 - 2432
(2012/10/30)
-
- Asymmetric hydrogenation of α- Or β-acyloxy α,β- unsaturated phosphonates catalyzed by a Rh(i) complex of monodentate phosphoramidite
-
The Rh(i) complex of a monodentate phosphoramidite bearing a primary amine moiety (DpenPhos) has been disclosed to be highly efficient for the asymmetric hydrogenation of a variety of α- or β-acyloxy α,β- unsaturated phosphonates, providing the corresponding biologically important chiral α- or β-hydroxy phosphonic acid derivatives with excellent enantioselectivities (90->99% ee).
- Zhang, Jinzhu,Dong, Kaiwu,Wang, Zheng,Ding, Kuiling
-
supporting information; experimental part
p. 1598 - 1601
(2012/03/22)
-