4-Phosphorinanones. II

Welcher, Richard P.; Day, Nancy E.

doi:10.1021/jo01052a083

Cited by 45 publications

(30 citation statements)

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“…In our hands, the solventless reaction of PhPH 2 with Scheme 2 dibenzylideneacetone (i.e. the literature route 1 to Ph L b ) gave several unidentified products in addition to Ph L b but, by employing MeCN as solvent and an acid catalyst, only isomers of Ph L b were observed.…”

Section: Ligand Synthesismentioning

confidence: 77%

“…31 P{ 1 H} NMR (CDCl 3 ): d = −2.2 (s, meso), −5.6 (s, rac). 1 H NMR (CDCl 3 ): d = 7.40-7.00 (13H, m, Ar), 6.82-6.68 (2H, m, Ar), 3.90-3.65 (2H, m, CH), 3.20-2.80 (4H, m, CH 2 ). m/z (EI) 344 (M + ).…”

Section: Preparation Of 126-triphenyl-4-phosphorinanone ( Ph L B )mentioning

confidence: 99%

“…31 P{ 1 H} NMR (CDCl 3 ): d = 17.9 (s). 1 H NMR (CDCl 3 ): d = 7.45-7.10 (10H, m, Ar), 3.33-3.14 (2H, m, CH), 2.92 (2H, td, J(HH) 14 Hz, J(HH) 7 Hz, CH 2 ), 2.79-2.57 (2H, m, CH 2 ), 0.64 (9H, d, 2 J(PC) 11 Hz, CH 3 ). 13 C NMR (CDCl 3 ): d = 208.3 (s, CO), 143.7 (d, 2 J(PC) 9 Hz, ipso-C), 128.9 (s), 128.3 (d, 3 J(PC) 9 Hz), 126.8 (s), 50.2 (d, 2 J(PC) 11 Hz, CH 2 ), 40.8 (d, 1 J(PC) 20 Hz, CHPh), 30.6 (d, 1 J(PC) 20 Hz, C(CH 3 ) 3 ), 28.4 (d, 2 J(PC) 11 Hz, CH 3 ).…”

Section: Preparation Of 1-cyclohexyl-26-diphenyl-4-phosphorinanone ( ...mentioning

confidence: 99%

“…31 P{ 1 H} NMR (CDCl 3 ): d = 42.2 (s). 1 H NMR (CDCl 3 ): d = 7.97-7.89 (4H, m, Ar), 7.48-7.38 (6H, m, Ar), 3.40 (4H, dt, 2 J(HH) 15 Hz, J(PC) 5 Hz, CH 2 ), 2.44 (4H, dt, 2 J(HH) 15 Hz, J(PC) 9 Hz, CH 2 ), 1.86 (12H, t, J(PC) 9 Hz, CH 3 ), 1.24 (12 H, t, J(PC) 6 Hz, CH 3 ). 13 C NMR (CDCl 3 ): d = 135.1 (s), 130.3 (s), 127.5 (s), 55.3 (s, CH 2 ), 38.3 (t, J(PC) 8 Hz, P-C), 31.7 (t, J(PC) 10 Hz, CH 3 ), 29.4 (s, CH 3 ).…”

Section: Preparation Of Trans-[pdcl 2 (L a ) 2 ] (1)mentioning

confidence: 99%

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Bulky 4-phosphacyclohexanones: diastereoselective complexations, orthometallations and unprecedented [3.1.1]metallabicycles

et al. 2006

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The 4-phosphacyclohexanones, 2,2,6,6-tetramethyl-1-phenyl-4-phosphorinanone (La), 1,2,6-triphenyl-4-phosphorinanone ((Ph)Lb), 1-cyclohexyl-2,6-diphenyl-4-phosphorinanone ((Cy)Lb) and 1-tert-butyl-2,6-diphenyl-4-phosphorinanone ((Bu)Lb) have been made by modifications of literature methods. Phosphines (R)Lb are each formed as mixtures of meso- and rac-diastereoisomers. Isomerically pure rac-(Ph)Lb, rac-(Cy)Lb and meso-(Bu)Lb can be isolated by recrystallisation from MeCN. Heating mixtures of isomers of (R)Lb with TsOH leads to isomerisations to give predominantly the meso-(R)Lb. The complex trans-[PdCl2(La)2] (1) is readily made from [PdCl2(NCPh)2] but the analogous platinum complex 2 has not been detected and instead, cyclometallation at the 3-position (alpha to the ketone) in the phosphacycle occurs to give trans-[PtCl(La)(La-3H)] (3) (where La-3H = La deprotonated at the 3-position) featuring a [3.1.1]metallabicycle as confirmed by X-ray crystallography. The analogous palladabicycle 4 has been detected upon treatment of 1 with Et3N in refluxing toluene. The type of complex formed by (R)Lb depends on which diastereoisomer (meso or rac) is involved. rac-(Ph)Lb (a mixture of R,R- and S,S-enantiomers, labelled alpha and beta) forms trans-[MCl2(rac-(Ph)Lb)2], M = Pd (5) or Pt (6), as mixtures of diastereoisomers (alphaalpha/betabeta and alphabeta forms). The structure of alphaalpha-6 has been determined by X-ray crystallography. Ligand competition experiments monitored by 31P NMR showed that Pd(II) and Pt(II) have a significant preference to bind rac-(Ph)Lb over meso-(Ph)Lb. meso-(Bu)Lb reacts with [PtCl2(NCBu(t))2] under ambient conditions to give the binuclear complex [Pt2Cl2(meso-(Bu)Lb-2'H)2] (7) where orthometallation has occurred on one of the exocyclic phenyl substituents as confirmed by X-ray crystallography. rac-(Bu)Lb reacts with [PtCl2(NCBu(t))2] to give a mononuclear cyclometallated species assigned the structure trans-[PtCl(rac-(Bu)Lb-2'H)((Bu)Lb)] (8) on the basis of its 31P NMR spectrum. rac-(Cy)Lb reacts with [PtCl2(NCBu(t))2] in refluxing toluene to give trans-[PtCl2(rac-(Cy)Lb)2] (9) and the crystal structure of alphabeta-9 has been determined.

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Section: Ligand Synthesismentioning

confidence: 77%

Section: Preparation Of 126-triphenyl-4-phosphorinanone ( Ph L B )mentioning

confidence: 99%

Section: Preparation Of 1-cyclohexyl-26-diphenyl-4-phosphorinanone ( ...mentioning

confidence: 99%

Section: Preparation Of Trans-[pdcl 2 (L a ) 2 ] (1)mentioning

confidence: 99%

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Bulky 4-phosphacyclohexanones: diastereoselective complexations, orthometallations and unprecedented [3.1.1]metallabicycles

et al. 2006

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“…Moreover, (90), R -= H, can be methylated or acylated to the stable cc-acylylide (91). The bromination of (89) to (92) with N-bromosuccinimide, followed by H3P04-catalysed dehydrobromination, leads to almost quantitative yields of the diene salts ( The question of whether this stabilization of (82) is due to the formation of a delocalized rr-electron system (through conjw gation at the phosphorus atom) or to resonance stabilization as postulated by Dewor (the phosphorus atom acts as an 1931 G. Murk/, Habilitation Thesis, Universitiit Wurzburg, 1963.…”

Section: Q -P -Q Omentioning

confidence: 99%

Heterocycles Containing Phosphorus

Märkl

1965

Angew. Chem. Int. Ed. Engl.

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found the force constant of the Si-S bond to be ksi.s --2.28 mdyne/A, and the absorption region of the Si-S bond (see also 1561 and 1601) was found to be from 520 to 400 cm-1. The force constant was determined for C13SiSH with the aid of the value of ksi-ci -= 2.46 mdyne/A calculated by Siebert 1681 for (CH,)3SiSCI. It was concluded from the close resemblance of the spectra that ksi.s == 2.28 mdyne/A is valid for all silicon-sulfur compounds, any deviations being only slight. This value agrees closely with the theoretical value of 2.22 mdyne/A calculated by Siebert (691 for the Si-S single bond, showing that Si-S bonds possess no appreciable double-bond character. These results were fully corroborated by subsequent investigations 170-731.

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The Wittig Reaction

Maercker

2011

Organic Reactions

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In 1953 Wittig and Geissler found that reaction of benzophenone with methylenetriphenylphosphorane gave 1,1‐diphenylethylene and triphenylphosphine oxide in almost quantitative yield; the phosphine had been prepared from triphenylmethylphosphonium bromide and phenyl lithium. The discovery led to the development of a new method for the synthesis of olefins, under the name Wittig reaction. One advantage of this new method is that the carbonyl group is replaced specifically by a carbon‐carbon double bond without the formation of isomeric olefins. In contrast, the older method of converting carbonyl compounds to olefins using the Grignard reaction usually give a mixture of isomeric olefins. Another advantage is the Wittig reaction is carried out under mild conditions. Discussions of modern techniques for the preparation of methylene phosphoranes are included in this review.

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4-Phosphorinanones. II

Cited by 45 publications

References 0 publications

Bulky 4-phosphacyclohexanones: diastereoselective complexations, orthometallations and unprecedented [3.1.1]metallabicycles

Bulky 4-phosphacyclohexanones: diastereoselective complexations, orthometallations and unprecedented [3.1.1]metallabicycles

Heterocycles Containing Phosphorus

The Wittig Reaction

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