The "phospha-Wittig" reaction: a new method for building phosphorus-carbon double and single bonds from carbonyl compounds

Marinetti, Angéla; Bauer, Siegfried; Ricard, Louis; Mathey, François

doi:10.1021/om00117a040

Cited by 85 publications

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“…Polyheteroaromatic structures based on the phosphole motif (I; Figure 1) have achieved a considerable degree of maturity and found application, for example, in organic light-emitting diodes (OLEDs); [4] phosphorus analogues of polyphenylvinylenes (II) [5] and oligoacetylenes (III) [6] have also been reported. Considering the reliability of the Wittig reactions for the conversion of aldehydes and ketones into alkenes, we were intrigued by the option to use the analogous phospha-Wittig-Horner (pWH) reaction [8][9][10] to prepare P-containing oligoacetylenes from appropriate acetylenic ketones. [7] In contrast to the plethora of synthetic procedures that are available for the preparation of pure hydrocarbons, the synthetic arsenal for the construction of I-III is limited.…”

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confidence: 99%

Cascade Reactions Forming Highly Substituted, Conjugated Phospholes and 1,2‐Oxaphospholes

2012

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Dedicated to Professor Peter J. Garratt on the occasion of his 78th birthday Highly unsaturated hydrocarbons [1] based on aromatics, alkenes, acetylenes, and combinations thereof are organic semiconductors. As such, they are interesting both from a basic research viewpoint [2] and in terms of their applications in electronics and photonics devices. [3] The replacement of carbon centers of such compounds by heavier low-valent main group elements, phosphorus in particular, has become increasingly popular. Polyheteroaromatic structures based on the phosphole motif (I; Figure 1) have achieved a considerable degree of maturity and found application, for example, in organic light-emitting diodes (OLEDs); [4] phosphorus analogues of polyphenylvinylenes (II) [5] and oligoacetylenes (III) [6] have also been reported. In all examples depicted in Figure 1, phosphorus inclusion greatly alters the electronic properties of the compounds compared to all-carbon-based analogues, and also offers a number of options for postsynthetic manipulations, such as metal complexations or oxidations. [7] In contrast to the plethora of synthetic procedures that are available for the preparation of pure hydrocarbons, the synthetic arsenal for the construction of I-III is limited. Considering the reliability of the Wittig reactions for the conversion of aldehydes and ketones into alkenes, we were intrigued by the option to use the analogous phospha-Wittig-Horner (pWH) reaction [8][9][10] to prepare P-containing oligoacetylenes from appropriate acetylenic ketones. Whereas traditional phosphonium ylides react with diacetylenic ketones exclusively in a 1,2-addition, which makes Wittigtype reactions a reliable tool for the preparation of 1,1diethynylethenes, [11,12] herein we demonstrate that a pWH reagent 1 exhibits a completely different reactivity. The observed 3,4-addition initiates a cascade of reactions that ultimately leads to the formation of either penta-substituted bis-phospholes or 2,5-dihydro-1,2-oxaphospholes, depending on the substituent at the acetylene termini of the diethynylketone (Scheme 1).As with all Wittig-type reactions, the pWH reaction is also initiated under basic conditions, in this case, by the addition of lithium diisopropylamide (LDA). The Li salt of 1 [9] is added to 1,5-bis(TES)-penta-1,4-diyne-3-one (2 a, TES = SiEt 3 ), [13,14] resulting in a red solution from which a bright red product 3 can be isolated in 57 % yield after silica gel chromatography. Mass spectrometric analysis of the product indicates that no simple pWH reaction occurred, as the observed molecular weight (m/z = 1159.15577, corresponding to C 43 H 60 O 9 P 2 Si 3 W + Ag) suggests that both P units of the pWH reagent are still present in the product and that 1 has reacted with two equivalents of ketone 2 a. Consistently, the 31 P NMR spectrum features two phosphorus centers (d( III P) = 167.4 ppm, d( V P) = 6.8 ppm), which couple to each other with J P-P = 63 Hz. A high degree of unsaturation can be expected from the presence of 11 quaternary c...

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Cascade Reactions Forming Highly Substituted, Conjugated Phospholes and 1,2‐Oxaphospholes

2012

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“…In addition, tungsten carbonyl complexes have been used to stabilize alkyl primary phosphines that have not been observed in the free state [11b, 30] and primary alkynyl and allenylphosphines that are otherwise highly unstable [11b, 31]. Mathey has shown that [W(CO) 5 (RPH 2 )] forms when 7-phosphanorbornadiene complexes of tungsten pentacarbonyl are reacted with dihydrogen under 20 bar pressure at 150 °C [32], and also that primary mono-phosphine complexes of both tungsten and molybdenum can be used to prepare metal-bound Phospha-Wittig reagents that react further to give phosphaalkenes [33]. Furthermore [M(CO) 5 [35] gave a comparable 1 J PH coupling constant of 328.0 Hz.…”

Section: Molybdenum and Tungsten Carbonyl Complexes Of The Fluorescenmentioning

confidence: 99%

Air-stable fluorescent primary phosphine complexes of molybdenum and tungsten

Davies

Wallis

Harrington

et al. 2016

Journal of Coordination Chemistry

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Here we report a study on the reactivity of the fluorescent air-stable primary phosphine 8-((4-phosphino)phenyl)-4,4-dimethyl-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene 4 with [Mo (CO) 6 ], [W(CO) 6 ], [Mo(CO) 4 (piperidine)] and [W(CO) 4 (piperidine)] which yields the mono-phosphine [Mo(CO) 5 (4)] 5, [W(CO) 5 (4)] 6 and di-phosphine cis-[Mo(CO) 4 (4) 2 ] (7) and cis-[W(CO) 4 (4) 2 ] (9) complexes as the predominant products. In addition to the characterisation of these complexes by multinuclear NMR and IR spectroscopy, and mass spectrometry, the solid state structures of 6 and cis-7 have also been determined by single crystal X-ray diffraction. The photophysical properties of the complexes show that the incorporation of the phosphorus ligand has a limited effect on the absorption and emission profile of the Bodipy core and that they retain similar quantum yields to their parent Bodipy dyes. Small quantities of the by-products trans-[Mo(CO) 4 (4) 2 ] (7), cis-[Mo(CO) 4 (piperidine)(4)] (8) and cis-[W(CO) 4 (piperidine)(4)] (10) were also isolated and characterized.

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“…A serious limitation of this protocol is the need of bulky substituents to provide the phospha-Wittig reagents with sufficient stability. This hurdle was circumvented by the coordination of the phosphinidene group to a transition-metal-complex fragment, preferentially to pentacarbonyltungsten, which stabilizes the organophosphorus precursor as well as the resulting phosphaalkene [47,48] phane complexes in a process analogous to the HornerWittig reaction [49,50] (Scheme 33). A different type of reaction was observed when phosphinidene-σ 4 -phosphoranes arylP=PMe 3 (aryl = 2,6-Mes 2 C 6 H 3 or 2,4,6-tBu 3 C 6 H 2 ) were combined with selected o-quinones.…”

Section: Phosphinidene Transfer From Phospha-wittig Reagentsmentioning

confidence: 99%

Phospha‐ and Arsaalkenes RE=C(NMe₂)₂ (E = P, As) as Novel Phosphinidene‐ and Arsinidene‐Transfer Reagents

Weber

2007

Eur J Inorg Chem

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Phosphinidenes (phosphanylidenes) (RP) are electronically and coordinatively unsaturated phosphorus compounds, which, as six-electron species, are formally analogous to the more familiar carbenes and nitrenes. In contrast to carbenes (CR 2 ), the extremely reactive phosphinidenes cannot be isolated without decomposition. Thus, our knowledge on phosphinidenes is mainly limited to trapping reactions and quantum-chemical calculations. There are a number of synthetic methods for phosphinidenes available, for example photolysis or thermolysis of cyclic phosphanes and oligophosphanes,

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The "phospha-Wittig" reaction: a new method for building phosphorus-carbon double and single bonds from carbonyl compounds

Cited by 85 publications

References 0 publications

Cascade Reactions Forming Highly Substituted, Conjugated Phospholes and 1,2‐Oxaphospholes

Cascade Reactions Forming Highly Substituted, Conjugated Phospholes and 1,2‐Oxaphospholes

Air-stable fluorescent primary phosphine complexes of molybdenum and tungsten

Phospha‐ and Arsaalkenes RE=C(NMe₂)₂ (E = P, As) as Novel Phosphinidene‐ and Arsinidene‐Transfer Reagents

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The "phospha-Wittig" reaction: a new method for building phosphorus-carbon double and single bonds from carbonyl compounds

Cited by 85 publications

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Cascade Reactions Forming Highly Substituted, Conjugated Phospholes and 1,2‐Oxaphospholes

Cascade Reactions Forming Highly Substituted, Conjugated Phospholes and 1,2‐Oxaphospholes

Air-stable fluorescent primary phosphine complexes of molybdenum and tungsten

Phospha‐ and Arsaalkenes RE=C(NMe2)2 (E = P, As) as Novel Phosphinidene‐ and Arsinidene‐Transfer Reagents

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Phospha‐ and Arsaalkenes RE=C(NMe₂)₂ (E = P, As) as Novel Phosphinidene‐ and Arsinidene‐Transfer Reagents