Online citations, reference lists, and bibliographies.
← Back to Search

The Value Of 2 J P–CO As A Diagnostic Parameter For The Structure And Thermal Reactivity Of Carbonyl-stabilised Phosphonium Ylides

R. Aitken, Youcef Boubalouta, D. Chang, Lee P. Cleghorn, I. P. Gray, N. Karodia, Euan J. Reid, A. Slawin
Published 2017 · Chemistry

Cite This
Download PDF
Analyze on Scholarcy
Share
Abstract A survey of 20 carbonyl-stabilised phosphonium ylides with recently reported X-ray structures shows a strong correlation between the C P to C O torsion angle and the value of 2JP–CO, with high values being associated with an anti configuration and low with syn. Seven new X-ray structural determinations are reported, several for types of ylide not crystallographically characterised before, and these also conform to this pattern. The value of 2JP–CO is then correlated with whether or not thermal extrusion of Ph3PO occurs to give alkynes for over 200 ylides and an empirical rule developed that the extrusion never occurs for ylides where this value is > 11 Hz. This is used to rationalise the anomalous behaviour of some trioxo ylides and cyclic ylides, two of which afford cycloalkynes, isolated after rearrangement as the isomeric 1,3-dienes. The rule also holds for a family of novel highly fluorinated ylides which afford fluorinated alkynes in good yield upon flash vacuum pyrolysis.
This paper references
10.1021/JA00796A077
Carbon-13 nuclear magnetic resonance of organophosphorus compounds. VII. Probing the phosphorus-carbon ylide bond
George A. Gray (1973)
10.1002/JLAC.199719970423
Flash‐Vacuum Pyrolysis of Stabilised Phosphorus Ylides, 9. Preparation and pyrolysis of β,γ‐dioxo ylides, β,β′,γ,γ′‐Tetraoxo Ylides and Hexaoxo Bis(ylides)
R. Aitken (1997)
10.1021/JO952079+
Photoaddition of Alkenes to Conjugated α-Diketones: Tandem Cyclizations Leading to Tetrasubstituted Furans1a
A. Mukherjee (1996)
10.3987/COM-13-S(S)70
FORMATION OF UNEXPECTED HETEROCYCLIC PRODUCTS FROM PYROLYSIS OF THIOCARBONYL STABILISED PHOSPHONIUM YLIDES (Dedicated to Professor Victor Snieckus on the occasion of his 77th birthday)
R. Aitken (2014)
10.1016/J.MOLSTRUC.2011.08.022
Molecular structures and preferred conformations of stabilized keto diester phosphonium ylides
F. Castañeda (2011)
10.1080/10426500390228657
Preferred Conformations of Stabilized Phosphorus Ylides
F. Castañeda (2003)
10.1021/JO01036A020
A New Synthesis of Cyclic Ketones1
H. House (1963)
10.1107/S0108270100016012
Methyl, ethyl, isopropyl and tert-butyl 3-oxo-2-(triphenylphosphoranylidene)butyrates, a common pattern for a preferred conformation.
F. Castañeda (2001)
10.1107/S0108270108018246
Favoured conformations of methyl isopropyl, ethyl isopropyl, methyl tert-butyl, and ethyl tert-butyl 2-(triphenylphosphoranylidene)malonate.
F. Castañeda (2008)
10.1039/B9NJ00528E
Cascade synthesis of new tetracyclic heteroaromatic thieno[2,3-b]pyridine-containing ring systems
R. Aitken (2009)
10.1002/anie.201107485
Arynes and cyclohexyne in natural product synthesis.
C. Gampe (2012)
10.1016/S0040-4039(01)82792-1
Nachweis behinderter rotation bei stabilen triphenylphosphinalkylenen.
H. Bestmann (1966)
10.1107/S0108270107010542
Differences in the crystal structures of two dialkyl diester triphenylphosphonium ylids.
F. Castañeda (2007)
10.1107/S0108270105015064
3-(Triphenylphosphoranylidene)pentane-2,4-dione and diethyl 2-(triphenylphosphoranylidene)malonate.
F. Castañeda (2005)
10.1021/JO970092J
NOVEL AND FACILE SYNTHESES OF ALKENYL, ALKYNYL, AND ARYL 1,2-DIKETONES
A. R. Katritzky (1997)
10.1002/CBER.19620950631
Reaktionen mit Phosphin‐alkylenen, II. C‐Acylierung von Phosphin‐alkylenen. Ein neuer Weg zur Synthese von Ketonen
H. J. Bestmann (1962)
10.1021/JO00128A038
NOVEL AND CONVENIENT ROUTES TO FUNCTIONALIZED ALKYNYL KETONES FROM 1-(BENZOTRIAZOL-1-YL)PROPARGYL ETHYL ETHERS
A. R. Katritzky (1995)
10.1071/CH9780327
Methyleneketenes and methylenecarbenes. XI. Rearrangements of cycloalkylidenecarbenes
G. Baxter (1978)
10.1016/S0040-4039(00)81929-2
Umwandlung von α-aminosäuren in α-diketone über oxazolin-zwischenstufen
J. Leyendecker (1983)
10.1071/CH9891161
Structural Investigations of Phosphoranes. A Single-Crystal X-Ray-Analysis of 1-Ethoxycarbonyl-2-oxopropylidene-triphenylphosphorane
A. Abell (1989)
10.1039/JR9620002333
448. A new synthesis of acetylenes. Part I
S. T. Gough (1962)
10.1039/P19960000485
Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 8. Preparation of symmetrical and unsymmetrical 1,3-diynes from alkynoyl ylides and oxalyl diylides
R. Aitken (1996)
10.1039/A701427I
Flash vacuum pyrolysis of stabilised phosphorus ylides. Part10.1 Generation of 2-methylstyrylalkynes and theirthermal cyclisation to 2-alkenylnaphthalenes
R. Aitken (1997)
10.1080/10426500802077242
Comparison of Conformations of Diesters of Stabilized Phosphonium Ylides in Solution and in the Crystal
F. Castañeda (2008)
10.1039/B110243E
Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 17. Preparation of aliphatic amino acid derived γ-alkoxycarbonylamino-β-oxo ylides and pyrolysis to give α,β-acetylenic γ-amino acid and GABA analogues
R. Aitken (2002)
10.1055/S-1987-27835
A facile synthesis of perfluoro-and ω-chloroperfluoro-1- pentafluorophenyl-1-alkynes
Y. Shen (1987)
10.1021/jo801716z
New gas-phase cascade reactions of stabilized phosphorus ylides leading to ring-fused indoles and to quinolines.
R. Aitken (2008)
10.1016/S0040-4039(01)96401-9
Ylide structure. V. Medium effects on phosphorane rotational equilibria: steric inhibition to solvation.
J. Snyder (1971)
10.1007/BF00845493
Intramolecular acylation of phosphorylides and a new route for the synthesis of α-substituted cyclopentanones
L. D. Bergelson (1963)
10.1039/P19940002473
Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 6. Pyrolysis of substituted cinnamoyl ylides as a route to conjugated enynes
R. Aitken (1994)
10.1039/C39880000874
Intramolecular Wittig reaction of α,α′-dioxocycloalkylidenetributylphosphoranes: formation and trapping of cycloalkyn-2-ones with five- and six-membered rings
Hidenobu Ohmori (1988)
10.1016/S0040-4039(00)75643-7
Proton nmp spectra of β-carbonyl phosphonium ylids
F. J. Randall (1968)
10.1002/RECL.19881071202
Thermal rearrangements of alkynes under FVP conditions. the acetylene-methylenecarbene rearrangement
R. C. Brown (2010)
10.1039/P19940002455
Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 3. Preparation of o-methoxyphenyl- and o-methylsulfanylphenyl-alkynes and their cyclisation to benzofurans and benzothiophenes
R. Aitken (1994)
10.1021/JO01285A089
Bis(pentafluorophenyl)acetylene and 2,3,4,5,6-pentafluorodiphenylacetylene
R. Filler (1967)
10.1016/J.MOLSTRUC.2008.12.016
Conformer determination of stabilized triphenyl phosphonium acyl ylides by infrared spectroscopy
C. A. Bunton (2009)
10.1016/S0040-4020(01)93736-6
Phosphonium salts and phosphoranes—VI
J. Brittain (1979)
10.1002/EJOC.201000733
P‐Stereogenic Phosphorus Compounds: Effect of Aryl Substituents on the Oxidation of Arylmethylphenylphosphanes under Asymmetric Appel Conditions
K. V. Rajendran (2010)
10.1039/P19940001281
Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 1. Preparation of aliphatic and terminal alkynes
R. Aitken (1994)
10.1002/CBER.19580910234
Phosphororganische Verbindungen, XV. Darstellung einiger neuer Phosphin‐ und Arsinalkylene
L. Horner (1958)
10.1002/CBER.19610941127
Synthese von α.β-Acetylencarbonsäuren durch innermolekulare Wittig-Reaktion
G. Maerkl (1961)
10.1021/JO990342R
A Study Directed to the Asymmetric Synthesis of the Antineoplastic Macrolide Acutiphycin under Enantioselective Acyclic Stereoselection Based on Chiral Oxazaborolidinone-Promoted Asymmetic Aldol Reactions.
Syun-ichi Kiyooka Si (1999)
10.1039/A905747A
The solid state conformation of oxo stabilised ylides: X-ray structures of four new polyoxo phosphorus ylides
R. Aitken (2000)
10.1021/JO00305A013
Synthesis and deprotection of [1-(ethoxycarbonyl)-4-[(diphenylmethoxy)carbonyl]-1-methyl-2-oxobutyl]triphenylphosphonium chloride: a key intermediate in the Wittig reaction between a cyclic anhydride and a stabilized ylide
A. Abell (1990)
10.1021/JA072925L
Synthesis of P-stereogenic phosphorus compounds. Asymmetric oxidation of phosphines under Appel conditions.
E. Bergin (2007)
10.1039/P19940002461
Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 4. Stepwise construction of terminal 1, 3-diynes, conjugated diacetylenic esters and a triacetylenic ester
R. Aitken (1994)
10.1002/CHEM.200501078
Fluorine segregation in crystalline materials: structural control and solid-state [2+2] cycloaddition in CF(3)-substituted tetrathiafulvalene derivatives.
O. Jeannin (2006)
10.1021/JO01352A010
Phosphinemethylenes.1 II. Triphenylphosphineacylmethylenes
F. Ramírez (1957)
10.1055/S-1995-4094
Chemoselective Oxidation of Carbon-Carbon Double or Triple Bonds to 1,2-Diketones with DMSO-Based Reagents
M. S. Yusubov (1995)
10.1002/EJOC.201000143
Unexpected rearrangement leading to formation of a 1,3-Bis(triphenylphosphonio)prop-1-en-3-idyl carboxylate
R. Aitken (2010)
10.1039/A807455K
Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 14.1 Tandem cyclisation of intermediate aryloxy and arylthio radicals leading to tri- and tetra-cyclic aromatic heterocycles
R. Aitken (1998)
10.5012/JKCS.2011.55.1.038
X-ray and Spectroscopy Studies of Mercury (II) and Silver (I) Complexes of α-Ketostabilized Phosphorus Ylides
K. Karami (2011)
10.1134/S107042800702008X
Phosphonium-iodonim ylides in nucleophilic substitution reactions
E. Matveeva (2007)
10.1080/10426500600887396
Conformational Differences in Stabilized Diketo and Diester Phosphonium Ylides in a Solid and in Solution
F. Castañeda (2007)
10.1021/ja00436a030
Nuclear magnetic resonance studies. 5. Properties of phosphorus-carbon ylides
T. A. Albright (1976)
10.1021/JA00214A034
Benzyne, cyclohexyne, and 3-azacyclohexyne and the problem of cycloalkyne versus cycloalkylideneketene genesis
C. Wentrup (1988)
10.1080/10426500802445373
A Common Conformation of Stabilized Triphenyl Phosphonium Ylidic Diesters with Bulky Alkoxy Groups
F. Castañeda (2009)
10.1039/JR9590003874
781. The reaction of witting reagents with phenyl isocyanate
S. Trippett (1959)
10.1021/ACS.ORGLETT.6B02278
Palladium-Catalyzed Ylidyl-Carbonylation of Aryl Halides To Produce α-Acylphosphoranes.
Xiaojun Guo (2016)
10.1016/J.MOLSTRUC.2009.07.028
Infrared spectroscopy and ab initio computation in conformer determination of keto ester and diketo triphenylphosphonium ylides
C. A. Bunton (2009)
10.1021/JA00252A028
An experimental and theoretical evaluation of the intramolecular reactions of cyclohexyne
J. Tseng (1987)
10.1021/IC060706F
Palladium complexes of a phosphorus ylide with two stabilizing groups: synthesis, structure, and DFT study of the bonding modes.
L. Falvello (2006)
10.3987/COM-15-S(T)14
NEW GAS-PHASE DOMINO PROCESSES LEADING TO BENZOPYRANONES AND BENZOFURANS
R. Aitken (2016)
10.1107/S0108270111027508
Conformations of diester triphenylphosphonium ylides with an ylidic ester or keto and ester ylidic groups.
F. Castañeda (2011)
10.1055/S-2000-6241
The Usefulness of Phosphorus Compounds in Alkyne Synthesis
Frédéric Eymery (2000)
10.1016/S0040-4020(99)00611-0
Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 16. Model studies for the construction of conjugated polymers
R. Aitken (1999)
10.1021/JO01015A015
The Reaction of Stable Phosphoranes with Acid Anhydrides. A New Synthesis of Acetylenic Ketones
P. Chopard (1965)
10.1002/ANIE.200503124
Bi-3H-diazirin-3-yls as precursors of highly strained cycloalkynes.
M. Al-Omari (2005)
10.1107/S0108270106051201
Cyano-stabilized triphenylphosphonium ylids.
F. Castañeda (2007)
10.1021/JA017908P
Mechanically induced solid-state generation of phosphorus ylides and the solvent-free Wittig reaction.
V. Balema (2002)
10.1039/P19940002467
Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 5. Selective extrusion of PH3PO from β,γ,β′-trioxo ylides to give diacylalkynes
R. Aitken (1994)
10.1016/S0040-4039(00)61098-5
Eine methode zurüberführung von acylakylidentriphenyl-phosphoranen in thioacylalkylidentriphenylphosphorane
H. J. Bestmann (1992)
10.1016/S0040-4039(01)98462-X
Ylide structure IV. Formylmethylenetriphenylphosphorane
J. Snyder (1970)
10.1016/S0040-4020(97)01007-7
One-step synthesis of dialkynyl-1,2-diones and their conversion to fused pyrazines bearing enediyne units
R. Faust (1997)
10.1107/S1600536807022623
4-Bromo­benzoyl­methyl­ene–triphenyl­phospho­rane ylide
S. J. Sabounchei (2007)
10.1016/S0040-4020(01)87069-1
Anodic oxidation of diarylacetylenes and diaryldiacetylenes: electrosynthesis of diaroyl-stilbenes and acetylenic α-and γ -diketones
M. Cariou (1991)
10.1002/EJOC.200390127
Synthesis and Pyrolytic and Kinetic Behaviour of β,δ′‐Dioxo‐Stabilised Phosphorus Ylides: Convenient Preparation of γ,δ‐Alkynyl Ketones and 2,3‐Functionalised Butadienes
R. Aitken (2003)
10.1016/S0040-4039(01)88121-1
Ylide structure. II. Rotational dynamics of methoxycarbonyl-methylenetriphenylphosphoranes by NMR.
H. I. Zeliger (1969)
10.1039/P29930000067
NMR of terminal oxygen. Part 10. 17O NMR spectra of carbonyl phosphonium ylides and diazocarbonyl compounds: resonance stabilization, bond order and excitation energy
H. Dahn (1993)
10.1021/NP990342M
Haliclonyne, a new highly oxygenated polyacetylene from the marine sponge Haliclona species.
L. Chill (2000)
10.1002/KIN.20170
Synthesis, thermal reactivity, and kinetics of stabilized phosphorus ylides, part 2: [(Arylcarbamoyl)(cyano)methylene]triphenylphosphoranes and their thiocarbamoyl analogues
R. Aitken (2006)
10.1039/b806787b
Bonding properties and bond activation of ylides: recent findings and outlook.
E. Urriolabeitia (2008)
10.1080/00397919608086738
Photochemical synthesis of carbazole derivatives
Malika Ibrahim-Ouali (1996)
10.1039/P19940001727
Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 2. Two-step conversion of acid chlorides into acetylenic esters and terminal alkynes
R. Aitken (1994)
10.1002/anie.201001137
Cyclohexyne cycloinsertion by an annulative ring expansion cascade.
C. Gampe (2010)
10.1080/10426500701509220
Cyano Triphenyl Phosphonium Ylides Stabilized by Ester or Keto Groups: Computed Conformations and Crystal Structures
F. Castañeda (2007)
10.1002/CBER.19610941213
Zur Existenz niedergliedriger Cycloalkine, I
G. Wittig (1961)



This paper is referenced by
Semantic Scholar Logo Some data provided by SemanticScholar