ChemInform Abstract: Ring Transformations of Phosphorus‐Containing Heterocycles. Part 5. The Formation of Phosphepine 1‐Oxides in the Reaction of Dihydrophosphinine 1‐Oxides with Dichlorocarbene.

Keglevich, Gyoergy; Petneházy, Imre; Toeke, L.; Janke, F.; Brlik, J.; Tóth, Gábor

doi:10.1002/chin.199015208

Cited by 1 publication

(2 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The addition of dichlorocarbene to the , -double-bond of the dihydrophosphinine oxides (1 4 ) afforded phosphabicyclo[4.1.0]heptane oxides 77 as intermediates giving phosphepine oxides 78 by the opening of the dichlorocyclopropane ring (Scheme 33) [41].…”

Section: Scheme 29mentioning

confidence: 99%

See 1 more Smart Citation

6-Membered P-Heterocycles: 1,2-Dihydro-, 1,2,3,6-Tetrahydro- and 1,2,3,4,5,6-Hexahydrophosphinine 1-Oxides

Keglevich

2006

COC

View full text Add to dashboard Cite

The members of a logically built P-heterocyclic family are discussed systematically to show a dynamically developing discipline of organophosphorus chemistry. Dichlorocyclopropanation of 2,5-dihydro-1H-phosphole oxides led to 3-phosphabicyclo[3.1.0]hexane 3-oxides that were useful intermediates for the synthesis of ring expanded products, such as 1,2-dihydrophosphinine oxides and 3-alkoxy-1,2,3,6-tetrahydrophosphinine oxides. Catalytic hydrogenation of 1,2-dihydrophosphinine oxides gave 1,2,3,4,5,6-hexahydrophosphinine oxides. Selective reduction of the , -doublebond of 1,2-dihydrophosphinine oxides via hydroboration led to 1,2,3,6-tetrahydrophosphinine oxides. Michael addition of >P(O)H species to the electron-poor double-bond of 1,2-dihydrophosphinine oxides afforded 1,2,3,6-tetrahydrophosphinine oxides with exocyclic P-function in position 3. Hydrogenation of these P-heterocycles led to the corresponding hexahydrophosphinine oxides. Stereostructure and conformation of the tetra-and hexahydrophosphinine oxides were elucidated by stereospecific NMR couplings and/or quantum chemical calculations. After deoxygenation, some of the above P-heterocycles were suitable P-ligands in transition metal complexes. The 1,2-dihydrophosphinine oxides were also useful in the synthesis of aromatic phosphinines, phosphepine derivatives and phosphabicyclo[2.2.2]octene oxides, as well as hetrocyclic -oxophosphoranes.

show abstract

Section: Scheme 29mentioning

confidence: 99%

“…Consequently, an alternative synthetic method had to be explored for the preparation of the triisopropylphenylhexahydrophosphinine oxide (41). In the first approach, introduction of the aryl group was attempted by substitution.…”

Section: Saturated Derivatives From 12-dihydrophosphinine Oxidesmentioning

confidence: 99%

6-Membered P-Heterocycles: 1,2-Dihydro-, 1,2,3,6-Tetrahydro- and 1,2,3,4,5,6-Hexahydrophosphinine 1-Oxides

Keglevich

2006

COC

View full text Add to dashboard Cite

show abstract

ChemInform Abstract: Ring Transformations of Phosphorus‐Containing Heterocycles. Part 5. The Formation of Phosphepine 1‐Oxides in the Reaction of Dihydrophosphinine 1‐Oxides with Dichlorocarbene.

Abstract: Addition of dichlorocarbene, generated from trichloromethane (III), to the chloro‐1‐methoxydihydrophosphinine oxides (I) and (II) gives a mixture of the phosphepin oxide (VI) and the phosphabicyclooctadiene oxide (VII) via the phosphabicycloheptenes (IV) and (V).

Cited by 1 publication

References 0 publications

6-Membered P-Heterocycles: 1,2-Dihydro-, 1,2,3,6-Tetrahydro- and 1,2,3,4,5,6-Hexahydrophosphinine 1-Oxides

6-Membered P-Heterocycles: 1,2-Dihydro-, 1,2,3,6-Tetrahydro- and 1,2,3,4,5,6-Hexahydrophosphinine 1-Oxides

Contact Info

Product

Resources

About