- 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
-
-
Read Online
- 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)
-
- Manganese-catalyzed oxophosphorylation reaction of carbon–carbon double bonds using molecular oxygen in air
-
A novel aerobic manganese-catalyzed oxophosphorylation reaction of carbon–carbon double bonds of styrene derivatives and vinyl ethers using diethyl H-phosphonates was developed. This direct transformation of alkenes to β-ketophosphonate readily proceeded at room temperature via the direct incorporation of molecular oxygen present in air (open flask).
- Yamamoto, Daisuke,Ansai, Hiromasa,Hoshino, Junichi,Makino, Kazuishi
-
p. 873 - 879
(2018/09/10)
-
- 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)
-
- 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)
-
- 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 0072; 0073; 0074; 0075; 0076
(2017/07/31)
-
- 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
-
p. 211 - 221
(2016/01/25)
-
- 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)
-
- 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)
-
- 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
-
supporting information
p. 1786 - 1789
(2015/04/14)
-
- 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
-
p. 5023 - 5029
(2015/05/27)
-
- 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)
-