The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(9), P. 7010 - 7018
Published: April 21, 2021
A three-component reaction involving arynes, trialkyl phosphites, and halides has been achieved under mild conditions. This transformation provides a direct synthetic approach to ortho-halogenated arylphosphonates, which could be rapidly converted diversely ortho-functionalized arylphosphorus compounds.
Language: Английский
Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(9), P. 1724 - 1818
Published: Jan. 20, 2020
Abstract Phosphorus‐substituted heterocycles represent an important class of organophosphorus compounds, which not only widely exist in biologically active pharmaceuticals, agrochemicals, but also have widespread applications material science and organic synthesis as ligands for transition metal complexes. The such compounds integrates the development new synthetic methods exploration efficient catalytic systems, reflects latest achievements organic, metal, photo even electrochemical catalysis, facilitates sufficient quantities related potential medicinal agents biological probes this area. Over past few decades, two major strategies been established toward phosphorus‐substituted heterocycles. This review summarizes recent progress field discusses reaction mechanisms detail. advantages limitations each subdivisional tactic are presented, opportunities still open outlined. magnified image
Language: Английский
Citations
144
Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(27), P. 14921 - 14930
Published: March 17, 2021
Abstract A highly enantiodivergent organocatalytic method is disclosed for the synthesis of atropisomeric biaryls via kinetic resolution inspired by a dipeptide‐phosphonium salt‐catalyzed Atherton–Todd (A‐T) reaction. This flexible approach led to both R ‐ and S ‐enantiomers fine‐tuning bifunctional phosphonium with excellent selectivity factors ( s ) up 1057 525, respectively. The potential newly synthesized O‐phosphorylated biaryl diols was illustrated axially chiral organophosphorus compounds. Mechanistic investigations suggest that halide catalyst differentiates between in‐situ‐generated P‐species in A‐T process, mainly involving phosphoryl chloride phosphoric anhydride, thus leading O‐phosphorylation reactions. Furthermore hydrogen bonding interactions catalysts phosphorus molecules were crucial asymmetric induction.
Language: Английский
Citations
59
Organic Letters, Journal Year: 2021, Volume and Issue: 23(5), P. 1541 - 1547
Published: Feb. 24, 2021
A Tf2O/DMSO-based system for the dehydrogenative coupling of a wide range alcohols, phenols, thiols, and thiophenols with diverse phosphorus reagents has been developed. This metal- strong-oxidant-free strategy provides facile approach to great variety organophosphinates thiophosphates. The simple reaction system, good functional-group tolerance, broad substrate scope enable application this method modification natural products direct synthesis bioactive molecules flame retardants.
Language: Английский
Citations
44
Organic Letters, Journal Year: 2020, Volume and Issue: 22(8), P. 3062 - 3066
Published: April 7, 2020
We report a direct and green electrochemical oxidative cross-dehydrogenative coupling reaction of N-heterocycles with hydrogen phosphoryl compounds under external oxidant-free conditions. Various phosphorylation products substituted carbazoles indoles are assembled in modest to excellent yields. A release process is preliminarily demonstrated H2 the sole byproduct. An imidazolium based ionic liquid selected as optimal electrolyte.
Language: Английский
Citations
45
ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(22), P. 13902 - 13912
Published: Nov. 1, 2021
Sulfur-stereogenic sulfoximines particularly with a free N-H unit exhibit intriguing chemical and biological activities, thus have received continuous attention from chemists. However, there are currently no examples of guiding catalytic asymmetric strategies available to directly access these molecules. Herein, we disclose an efficient practical protocol for the direct enantioenrichment sulfoximines, via bifunctional phosphonium salt-catalyzed desymmetrization triggered by Atherton–Todd reaction together further extended nucleophilic acyl substitution-type reaction. A series bearing assortment aromatic groups (70 examples) tolerated in this incidentally involving minority kinetic resolution (KR). The desymmetrized products can be easily transformed into chiral sulfoxides other classes active sulfur-stereogenic compounds. Mechanistic studies provided insights pathway suggesting desymmetrization/KR synergic process, also offered support on hydrogen-bonding interactions as key elements successful stereocontrol.
Language: Английский
Citations
35
Chemical Synthesis, Journal Year: 2021, Volume and Issue: unknown
Published: Jan. 1, 2021
Chemical Synthesis is an open access peer-reviewed journal publishing original research involving all areas of the chemical sciences. The aims to be premier resource seminal and insightful showcases for researchers in both academia industry, providing a platform inspiration future chemistry. intends serve as preeminent international chemistry has ambition among first choices chemists publication their discoveries.
Language: Английский
Citations
34
Organic Letters, Journal Year: 2020, Volume and Issue: 22(12), P. 4742 - 4748
Published: June 2, 2020
Addition of P-H species to carbonyl groups, namely the Pudovik reaction, normally delivers hydroxyl phosphorus compounds, along with phosphate byproducts in some cases. A few controllable systems starting from phosphites were set up mainly provide phosphates. Herein, we present a highly selective protocol phosphonate precursors leading phosphinate derivatives. Enantioenriched phosphinates successfully achieved chiral phosphine oxide precursors. Experimental and theoretical investigations conducted understand mechanistic details.
Language: Английский
Citations
38
Organic Letters, Journal Year: 2020, Volume and Issue: 22(15), P. 6143 - 6149
Published: July 10, 2020
We report a redox-neutral P(O)–N coupling reaction of P(O)–H compounds with azides via photoredox and copper catalysis, providing new access to useful phosphinamides, phosphonamides, phosphoramides. This transformation tolerates wide range nucleophilic functionalities including alcohol amine nucleophiles, which makes up for the deficiency classical nitrogen substitution reactions. As demonstration broad potential applications this methodology, late-stage functionalization diverse array azido-bearing natural products drug molecules, preliminary asymmetric reaction, continuous visible-light photoflow process have been developed.
Language: Английский
Citations
33
Green Chemistry, Journal Year: 2023, Volume and Issue: 25(11), P. 4528 - 4535
Published: Jan. 1, 2023
A photocatalytic phosphorylation of heteroatom nucleophiles has been achieved via the direct coupling phosphorus-centered radical cations with nucleophiles.
Language: Английский
Citations
12
Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(60), P. 14931 - 14935
Published: Aug. 27, 2021
An electrochemical three component cascade phosphorylation reaction of various heteroatoms-containing nucleophiles including carbazoles, indoles, phenols, alcohols, and thiols with Ph2 PH has been established. Electricity is used as the "traceless" oxidant water air are utilized "green" oxygen source. All kinds structurally diverse organophosphorus compounds P(O)-N/P(O)-O/P(O)-S bonds assembled in moderate to excellent yields (three categories products, 50 examples, up 97 % yield). A tentative free radical course put forward rationalize procedure.
Language: Английский
Citations
25