Simple Synthesis of Functionalized 2‐Phosphanaphthalenes

Mei, Yanbo; Wu, Dong-Jun; Borger, Jaap E.; Grützmacher, Hansjörg

doi:10.1002/anie.201802242

Cited by 22 publications

(23 citation statements)

References 66 publications

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“…[74] This compound can be easily further derivatized using arange of electrophiles such as ClP(O)Ph 2 or 2-chloropyridine.T he resulting neutral compounds can be used as new chelating ligands.Inaclosely related reaction, Caulton and co-workers have shown that tetrazines react readily with Na(OCP) under elimination of N 2 whereby various 1,2,4-diazaphosphinin-5olates are obtained as products. [74] This compound can be easily further derivatized using arange of electrophiles such as ClP(O)Ph 2 or 2-chloropyridine.T he resulting neutral compounds can be used as new chelating ligands.Inaclosely related reaction, Caulton and co-workers have shown that tetrazines react readily with Na(OCP) under elimination of N 2 whereby various 1,2,4-diazaphosphinin-5olates are obtained as products.…”

Section: Six-membered Heterocyclesmentioning

confidence: 99%

The Chemistry of the 2‐Phosphaethynolate Anion

2018

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In all likelihood the first synthesis of the phosphaethynolate anion, PCO , was performed in 1894 when NaPH was reacted with CO in an attempt to make Na(CP) accompanied by elimination of water. This reaction was repeated 117 years later when it was discovered that Na(OCP) and H are the products of this remarkable transformation. Li(OCP) was synthesized and fully characterized in 1992 but this salt proved to be too unstable to allow for a detailed investigation of its chemistry. It was not until the heavier analogues of this lithium salt were isolated, Na(OCP) and K(OCP) (both of which are remarkably stable and can be even dissolved in water), that the chemistry of this new functional group could be explored. Here we review the chemistry of the 2-phosphaethynolate anion, a heavier phosphorus-containing analogue of the cyanate anion, and describe the wide breadth of chemical transformations for which it has been thus far employed. Its use as a ligand, in decarbonylative and deoxygenative processes, and as a building block for novel heterocycles is described. In the mere twenty-six years since Becker first reported the isolation of this remarkable anion, it has become a fascinating reagent for the synthesis of a vast library of, often unprecedented, molecules and compounds.

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Section: Six-membered Heterocyclesmentioning

confidence: 99%

The Chemistry of the 2‐Phosphaethynolate Anion

2018

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“…[4a] Although the phosphanaphthalenes were first synthesized in the 1970s, they have recently re‐captured the attention of the scientific community. As a result, for instance, new synthetic strategies to fuse phosphanaphthalenes with oxazole rings and the improvement of their synthesis have been developed. In the following sections, we will particularly focus on larger linearly fused systems containing six‐membered phosphorus heterocycles.…”

Section: Phosphorus Heteroarenes: the Originmentioning

confidence: 99%

From Phosphaphenalenes to Diphosphahexaarenes: An Overview of Linearly Fused Six‐Membered Phosphorus Heterocycles

2019

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The chemistry of linearly fused systems based on sixmembered phosphorus heterocycles is currently experiencing an astonishing evolution. Even though the phosphorus analogs of naphthalene and anthracene were first synthesized in the late 1960s, laterally fused phosphorus heterocycles have recently demonstrated outstanding performances as biomarkers, [a] Scheme 2. Synthetic route to afford diphosphahexaarenes: a) CsF, Pd(PPh 3 ) 4 , CuI, 50°C/(8-bromonaphthalen-1-yl)tributylstannane; b) 1. tBuLi, -78°C, 2. PhPCl 2 , 3. H 2 O 2 , 0°C.

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“…Note, during the preparation of this manuscript, Grützmacher et al. reported one example of a phosphanaphthalene through N 2 elimination; however, the synthesis requires reaction times over several weeks to months at 80 °C . For accessing azaphosphinines, triazines and tetrazines should be ideal starting materials as they are electron‐deficient, known to undergo inverse‐electron‐demand hetero‐D.A.…”

Section: Figurementioning

confidence: 99%

Synthesis of Azaphosphinines by Directed Inverse‐Electron‐Demand Hetero‐Diels–Alder Reactions with Na(OCP)

Hansmann

2018

Chemistry A European J

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Herein, a straightforward synthetic approach towards azaphosphinines is reported. The synthesis of 1,3- and 1,4-aza-λ -phosphinines as well as 1,2,4-diaza-λ -phosphinines by inverse-electron-demand hetero-Diels-Alder reactions of sodium 2-phosphaethynolate [NaOCP] with triazines and tetrazines is studied. In the case of 1,2,4-triazines a hetero-D.A. reaction was developed, which relies on a new directing-group approach based on the complexation of sodium to form an ionic Do→Na-OCP tether. The first X-ray characterization data for aza-λ -phosphinines as well as the first phosphinine triflates are presented.

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Simple Synthesis of Functionalized 2‐Phosphanaphthalenes

Cited by 22 publications

References 66 publications

The Chemistry of the 2‐Phosphaethynolate Anion

The Chemistry of the 2‐Phosphaethynolate Anion

From Phosphaphenalenes to Diphosphahexaarenes: An Overview of Linearly Fused Six‐Membered Phosphorus Heterocycles

Synthesis of Azaphosphinines by Directed Inverse‐Electron‐Demand Hetero‐Diels–Alder Reactions with Na(OCP)

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