Synthesis of Silyl and Germyl Ketones

Brook, A. G.; Duff, J. W.; Jones, Peter; Davis, Nicole R.

doi:10.1021/ja00978a047

Cited by 217 publications

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“…All compounds absorb far into the visible, and all the visible transitions were strongly banded, as has been observed previously with acylmetalloid compounds (4,6). The extinction coefficients reported cannot be considered to be very accurate because of the demonstrable instability of the solutions, especially in light, but in all cases the band intensities are progressively larger, the longer the wavelength.…”

Section: Spectral Propertiessupporting

confidence: 64%

“…A further route to bis(metalloida1)ketones from the hydrolysis of 2,2-dimetalloidal-l,3-dithianes was explored, since the general method had been found useful for the synthesis of acyl-silanes and -germanes (6,14). With the exception of 2,2-bis(triphenylsily1)-1,3-dithiane, 9a, each of the disubstituted dithianes hydrolyzed in a benzene-acetonewater solvent mixture containing mercuric chloride and cadmium carbonate to give pink solutions containing bis(metalloidal)ketones, as shown by their characteristic ultraviolet absorption spectra.…”

Section: Ochomentioning

confidence: 99%

“…Research (1)(2)(3)(4)(5)(6) in these laboratories over a number of years has resulted in the preparation of a large number of acylsilanes and acylgermanes. ' The most striking features of these compounds are their remarkable spectral properties, both in the infrared and ultraviolet regions.…”

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confidence: 99%

“…46,1968 A similar procedure was used to synthesize bis(triphenylsilyl)ketone, 1. In this case, the preparation of the intermediate carbinol, 6, from triphenylsilyllithium and ethyl formate was complicated by the formation of substantial quantities of triphenylsilyltriphenylsiloxymethane, 7, which is the expected product of the well-studied "silylcarbinol to silyl ether" rearrangement (1 1, 12).…”

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confidence: 99%

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Bis(metalloidal)ketones

Brook¹,

Jones²,

Peddle³

1968

Can. J. Chem.

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A number of bis(sily1)-and bis(germy1)-ketones have been prepared by the oxidation of the corresponding carbinol or by the hydrolysis of the dithiane precursor. The ketones are all highly colored and their spectral properties are consistent with inductive interaction of both metalloid atoms with the carbonyl group. The reactions of bis(tripheny1germyl)ketone under various conditions have been studied and the results obtained are consistent with the intermediacy of triphenylgermyl radicals.Canadian Journal of Chemistry, 46, 2119 (1968) Research (1-6) in these laboratories over a number of years has resulted in the preparation of a large number of acylsilanes and acylgermanes.' The most striking features of these compounds are their remarkable spectral properties, both in the infrared and ultraviolet regions. Thus thecarbonyl n -t z* transitions of the acyl-silanes and -germanes show a marked bathochromic shift compared with those of their carbon counterparts, and the infrared carbonyl stretching wavelength in the metalloidal compounds is also significantly longer than in the analogous carbon compounds. In addition it has recently been shown (7, 8) that acylsilanes undergo unusual photochemical transformations.In view of the above results, it appeared of interest to synthesize compounds where the carbonyl group was flanked by two metalloid atoms, in order to gain further insight into the effect of adjacent metalloid atoms on the chemical and spectral properties of the carbonyl group. A preliminary account of the preparation and spectral properties of bis(triphenylsilyl)ketone, 1, and its germanium analog 2, has appeared (9) and in the present communication we wish to give full details of this work, together with an account of the synthesis and spectral properties of additional ketones, and a study of the chemical reactions of bis(triphenylgermyl)ketone, 2. 'We now favor usage of the term acylsilane instead of the formerly used a-silyl ketone to describe compounds with the structure Si-CO-. Preparation of Bis(metalloidal)ketonesBis(triphenylgermyl)ketone, 2, was prepared by the route shown in Fig. 1

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Section: Spectral Propertiessupporting

confidence: 64%

Section: Ochomentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Bis(metalloidal)ketones

Brook¹,

Jones²,

Peddle³

1968

Can. J. Chem.

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“…The dithiane route applicable for the synthesis of a wider range of acylsilanes was studied by Brook et al [24] and Corey et al [25] at the same time in 1967 (Equation (2)). The defect of the method is the use of a toxic mercury compound for the hydrolysis of the silylated dithianes.…”

Section: Introductionmentioning

confidence: 99%

Reactions of an Isolable Dialkylsilylene with Aroyl Chlorides. A New Route to Aroylsilanes

et al. 2016

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Abstract:The reactions of isolable dialkylsilylene 1 with aromatic acyl chlorides afforded aroylsilanes 3a-3c exclusively. Aroylsilanes 3a-3c were characterized by 1 H-, 13 C-, and 29 Si-NMR spectroscopy, high-resolution mass spectrometry (HRMS), and single-crystal molecular structure analysis. The reaction mechanisms are discussed in comparison with related reaction of 1 with chloroalkanes and chlorosilanes.

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Formal Asymmetric Synthesis of Pentalenolactone E and Pentalenolactone F-2. Construction of the Angular Diquinanoid δ-Lactone

Herrmann

Gais²,

Rosenstock

et al. 1998

Eur. J. Org. Chem.

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A formal asymmetric synthesis of pentalenolactone E (1b) and pentalenolactone F (1a) has been accomplished. Ozonolysis of the diphenyl‐substituted triquinane 3 and Kauffmann methylenation of ketone 5 with WOCl3‐2 MeLi yielded the unsubstituted triquinane 9. The crucial rearrangement of the linear triquinanoid lactone 11 to the angular triquinanoid lactone 14a was accomplished using orthoformate and acid in methanol. Subjecting triquinanes 14a/b to the selenoxide method gave triquinene 15. Homologation of γ‐lactone 15 to the angular diquinanoid δ‐lactone 2 via a Horner‐Wadsworth‐Emmons or Peterson reaction of hemiacetals 16a/b was, however, not successful. Chemoselective reduction of 14a afforded hemiacetals 21a/b, reaction of which with the phosphonate salt 17a ultimately led to the ketene dithioacetal 22. The angular intermediates 25a/b were obtained from 22 by reduction to give the linear hemiacetals 24a/b, which rearranged to the dithio ortholactones 25a/b in the presence of acid. Introduction of the double bond and deprotection were accomplished via selenation of 25a/b with N,N‐diethylbenzeneselenylamide and treatment of selenides 30a/b with silver nitrate. The unsaturated aldehydes 28 and 29 thus obtained were converted to 2 and 31, respectively, by oxidation with manganese dioxide in the presence of sodium cyanide, methanol and acetic acid. Alkene 2 was isolated by crystallization.

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Synthesis of Silyl and Germyl Ketones

Abstract: Procedures for the synthesis of a number of silyl and germyl ketones, by hydrolysis of the related 2-substituted 1,3-dithianes, are given. New ketones described include several trialkylgermyl compounds, acetyltrimethylsilane, and new bisketones.

Cited by 217 publications

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Bis(metalloidal)ketones

Bis(metalloidal)ketones

Reactions of an Isolable Dialkylsilylene with Aroyl Chlorides. A New Route to Aroylsilanes

Formal Asymmetric Synthesis of Pentalenolactone E and Pentalenolactone F-2. Construction of the Angular Diquinanoid δ-Lactone

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