Synthesis of α-Silyl Ketones <i>via</i> 1,3-Dithianes

Corey, E. J.; Seebàch, Dieter; Freedman, R.

doi:10.1021/ja00978a048

Cited by 210 publications

(58 citation statements)

References 2 publications

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“…[66] Its lithium salt reacts with aldehydes and ketones to form ketene dithioacetals 111, [67] which can be reduced with tetrafluoroboric acid and sodium borohydride to the corresponding 2-alkyl-1,3-dithianes 112. [68] Quite a few carbonyl derivatives (aldehydes and ketones) were thus converted to dithianes 112 which in their turn were reacted for 1 min with 2.5 mol equivalents of BrF 3 at 0 8C forming 1,1-difluoro-2-alkylalkanes 113 in good yields.…”

Section: Forming the Cf 2 Groupmentioning

confidence: 99%

Selective Reactions of Bromine Trifluoride in Organic Chemistry

Rozen

2010

Adv Synth Catal

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Although known for more than a century, bromine trifluoride is not a common reagent in day to day research work in organic chemistry. Its tendency to react exothermically with solvents containing Lewis base elements such as water, acetone or ethers distanced it from the mind of many. Still, under the proper conditions, it can perform quite a few selective reactions which are difficult to achieve by other reagents. We discuss in this review reactions which have been published in the last 30 years. They consist of fluorinating heteroatoms, substituting carbon-halogen bonds with carbon-fluorine bonds, syntheses of anesthetics, construction of the trifluoromethyl (CF 3 ) and the difluoromethylene (CF 2 ) groups, aromatic brominations and more.

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Section: Forming the Cf 2 Groupmentioning

confidence: 99%

Selective Reactions of Bromine Trifluoride in Organic Chemistry

Rozen

2010

Adv Synth Catal

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“…All acylmetalloids were prepared by previously described methods (6)(7)(8). Physicaldata ofnew acylmetalloids are listed in Table 3 and spectroscopic data are given in Table 4.…”

Section: Preparation Of Acylrnetalloidsmentioning

confidence: 99%

Photolysis of Acyl Group IV Metalloids: the Formation of Silyl Radicals

Brook¹,

Dillon²,

Pearce³

1971

Can. J. Chem.

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“…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%

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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Synthesis of α-Silyl Ketones via 1,3-Dithianes

Cited by 210 publications

References 2 publications

Selective Reactions of Bromine Trifluoride in Organic Chemistry

Selective Reactions of Bromine Trifluoride in Organic Chemistry

Photolysis of Acyl Group IV Metalloids: the Formation of Silyl Radicals

Bis(metalloidal)ketones

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