"First isolation and characterization of 1,2-oxaphosphetanes with three phenyl groups at the phosphorus atom in typical Wittig reaction using cyclopropylidenetriphenylphosphorane"
Wikipedia coverage
- Wittig reaction
- Oxaphosphetane - I will write this soon
Basic description
An oxaphosphetane is a molecule containing a four-membered ring with one phosphorus, one oxygen and two carbon atoms. In a 1,2-oxaphosphetane phosphorus is bonded directly to oxygen. 1,2-Oxaphosphetanes are rarely isolated but are important intermediates in the Wittig reaction and related reactions such as the Seyferth–Gilbert homologation and the Horner–Wadsworth–Emmons reaction.
Similar molecules
- oxetane
- phosphetane
- 2,2-dihydro-1,2-oxaphosphetane (pentavalent P, parent of Wittig oxaphosphetanes)
- 1,2-oxaphosphetane (trivalent P)
Sources of information
VKA, JNH papers on Wittig mechanism
- J. Am. Chem. Soc., 2006, 128 (7), pp 2394–2409 (full details and discussion)
- J. Am. Chem. Soc., 2005, 127 (39), pp 13468–13469 (nice summary)
Journal articles
- 1988: The stereochemistry of Wittig reactions of ylide-anions derived from semi-stabilized phosphonium ylides
- 1989: Oxaphosphetane pseudorotation: rates and mechanistic significance in the Wittig reaction
- 1994: Synthesis, Structure, and Thermolysis of a 1,5-Dioxa-4λ5-phosphaspiro[3.3]heptane: A Novel Pentacoordinate 1,2-Oxaphosphetane
- 1995: Stereoselectivity in the Wittig Reaction of Aromatic Ketones: Origin of Preference for the Olefin Geometry
- 1998: Observation of Pseudorotamers of Two Unconstrained Wittig Intermediates, (3RS,4SR)- and (3RS,4RS)-4-Cyclohexyl-2-ethyl-3,4-dimethyl-2,2-diphenyl-1,2λ5-oxaphosphetane, by Dynamic 31P NMR Spectroscopy: Line-Shape Analyses, Conformations, and Decomposition Kinetics
-
2002: A Wittig Reaction with 2-Furyl Substituents at the Phosphorus Atom: Improved (Z) Selectivity and Isolation of a Stable Oxaphosphetane Intermediate
(DOI = 10.1002/1099-0690(200204)2002:7<1143::AID-EJOC1143>3.0.CO;2-G) - 2002: First Isolation and Characterization of an Anti-Apicophilic Spirophosphorane Bearing an Oxaphosphetane Ring: A Model for the Possible Reactive Intermediate in the Wittig Reaction
- 2003: Dilithiated phosphazenes: scaffolds for the synthesis of olefins through a new class of bicyclic 1,2-oxaphosphetanes
- 2004: Molecular modeling of oxaphosphetane intermediates of wittig olefination reactions
- 2007: New possible ionic structures in Wittig reaction: Analysis of stability and rotation barriers by semiempirical PM3 method
- 2008: Dynamic NMR study of the oxaphosphetane complexation with lithium during the Wittig reaction
Websites
- http://www.organic-chemistry.org/namedreactions/wittig-reaction.shtm
- Alfa Aesar organophosphorus review
- http://www.springer.com/carey-sundberg/wadsworth_emmons/views/oxaphosphetane4a.html
- http://users.ox.ac.uk/~mwalter/web_05/resources/phos_chem/org_phosph_chem.shtml
- http://www.chm.bris.ac.uk/pt/harvey/postgradcc/exercises/wittig_exercise.htm – Professor Jeremy Harvey's Wittig modelling exercise
"First isolation and characterization of 1,2-oxaphosphetanes with three phenyl groups at the phosphorus atom in typical Wittig reaction using cyclopropylidenetriphenylphosphorane"
Wikipedia coverage
- Wittig reaction
- Oxaphosphetane - I will write this soon
Basic description
An oxaphosphetane is a molecule containing a four-membered ring with one phosphorus, one oxygen and two carbon atoms. In a 1,2-oxaphosphetane phosphorus is bonded directly to oxygen. 1,2-Oxaphosphetanes are rarely isolated but are important intermediates in the Wittig reaction and related reactions such as the Seyferth–Gilbert homologation and the Horner–Wadsworth–Emmons reaction.
Similar molecules
- oxetane
- phosphetane
- 2,2-dihydro-1,2-oxaphosphetane (pentavalent P, parent of Wittig oxaphosphetanes)
- 1,2-oxaphosphetane (trivalent P)
Sources of information
VKA, JNH papers on Wittig mechanism
- J. Am. Chem. Soc., 2006, 128 (7), pp 2394–2409 (full details and discussion)
- J. Am. Chem. Soc., 2005, 127 (39), pp 13468–13469 (nice summary)
Journal articles
- 1988: The stereochemistry of Wittig reactions of ylide-anions derived from semi-stabilized phosphonium ylides
- 1989: Oxaphosphetane pseudorotation: rates and mechanistic significance in the Wittig reaction
- 1994: Synthesis, Structure, and Thermolysis of a 1,5-Dioxa-4λ5-phosphaspiro[3.3]heptane: A Novel Pentacoordinate 1,2-Oxaphosphetane
- 1995: Stereoselectivity in the Wittig Reaction of Aromatic Ketones: Origin of Preference for the Olefin Geometry
- 1998: Observation of Pseudorotamers of Two Unconstrained Wittig Intermediates, (3RS,4SR)- and (3RS,4RS)-4-Cyclohexyl-2-ethyl-3,4-dimethyl-2,2-diphenyl-1,2λ5-oxaphosphetane, by Dynamic 31P NMR Spectroscopy: Line-Shape Analyses, Conformations, and Decomposition Kinetics
-
2002: A Wittig Reaction with 2-Furyl Substituents at the Phosphorus Atom: Improved (Z) Selectivity and Isolation of a Stable Oxaphosphetane Intermediate
(DOI = 10.1002/1099-0690(200204)2002:7<1143::AID-EJOC1143>3.0.CO;2-G) - 2002: First Isolation and Characterization of an Anti-Apicophilic Spirophosphorane Bearing an Oxaphosphetane Ring: A Model for the Possible Reactive Intermediate in the Wittig Reaction
- 2003: Dilithiated phosphazenes: scaffolds for the synthesis of olefins through a new class of bicyclic 1,2-oxaphosphetanes
- 2004: Molecular modeling of oxaphosphetane intermediates of wittig olefination reactions
- 2007: New possible ionic structures in Wittig reaction: Analysis of stability and rotation barriers by semiempirical PM3 method
- 2008: Dynamic NMR study of the oxaphosphetane complexation with lithium during the Wittig reaction
Websites
- http://www.organic-chemistry.org/namedreactions/wittig-reaction.shtm
- Alfa Aesar organophosphorus review
- http://www.springer.com/carey-sundberg/wadsworth_emmons/views/oxaphosphetane4a.html
- http://users.ox.ac.uk/~mwalter/web_05/resources/phos_chem/org_phosph_chem.shtml
- http://www.chm.bris.ac.uk/pt/harvey/postgradcc/exercises/wittig_exercise.htm – Professor Jeremy Harvey's Wittig modelling exercise