Diazo alkanes ketones

Polyfluoroalkyl- andperfluoroalkyl-substituted CO and CN multiple bonds as dipolarophiles. Dmzo alkanes are well known to react with carbonyl compounds, usually under very mild conditions, to give oxiranes and ketones The reaction has been interpreted as a nucleophilic attack of the diazo alkane on the carbonyl group to yield diazonium betaines or 1,2,3 oxadiazol 2 ines as reaction intermediates, which generally are too unstable to be isolated Aromatic diazo compounds react readily with partially fluorinated and perfluorinated ketones to give l,3,4-oxadiazol-3-ines m high yield At 25 °C and above, the aryloxa-diazolines lose nitrogen to give epoxides [111]... 

A neutral diazo compound can be considered as both a nucleophile and an electrophile. Thus, it can be substituted by the combination of an electrophilic moiety and a nucleophilic moiety (X+ Nu ") (Scheme 8). In practice, the diazomethyl group is transformed to the fluoromethyl group by treatment with hydrogen fluoride/pyridine mixture (70 30 w/w) (X = H Nu = F), or to the halofluoromethyl group by addition of A-halosuccinimide in the same medium (X = Cl, Br, I Nu = F), e.g. formation of l.16 The reaction can be performed on secondary diazo alkanes, diazo ketones or diazo esters.16 90 316... 

The importance of a-diazo ketones as synthetic intermediates has led to the development of a number of general methods for their preparation.5 Particularly popular approaches include the acylation of diazo alkanes and the base-catalyzed "diazo group transfer" reaction of sulfonyl azides with 8-dicarbonyl compounds.6-7 While direct diazo transfer to ketone enolates is usually not a feasible process,8-9 diazo transfer to simple ketones can be achieved in two steps by employing an indirect deformylative diazo transfer strategy in which the ketone is first formylated under Claisen condensation conditions, and then treated with a sulfonyl azide reagent such as p-toluenesulfonyl azide.6a,6c,9,i0,11... 

A diazo ester or alkane will react with a ketone, under Lewis acid catalysis, to give the homologated product. This reaction is most often used for one-carhon ring expansion, as illustrated hy the conversion of (166) to (167 equation 69). The regioselectivity of the (166) to (167) transformation, 98 2 in the example illustrated, was found to depend on both the diazoalkane and the Lewis acid used. With diazomethane and boron trifluoride, a 1 1 mixture of regioisomeric products was observed. 

Transition metal catalyzed decomposition of unsaturated a-diazo ketones or a-diazo esters is a powerful method for the synthesis of certain 2-oxobicyclo[n.l.0]alkanes. In contrast to the thermal (see Section 1.2.1.2.4.2.6.1.) and photochemical (see Section I.2.I.2.4.2.6.2.) methods, which have only been applied successfully in a few cases, the carbenoid version has been extensively utilized for the construction of simple or highly substituted bicyclic, tricyclic or higher systems of predictable stereochemistry (for reviews, see refs 2, 82, 320). Several of the cyclopropanes so obtained have been transformed further into natural products with diverse molecular skeletons. As examples and procedures have already been presented in Houben-Weyl, Vol. E19b, ppl088ffand 1271 ff, only some important aspects concerning the scope and limitation of the method as well as recent developments concerning its stereochemistry will be discussed here. 

Monohalo or dihalo alkanes, carboxylic acids, or ketones are obtained on treating diazoalkanes,1167 diazocarboxylic esters,1168 or diazo ketones with hydrogen halides or halogens. The reaction usually occurs at room temperature or below. However, preparative importance attaches only to the formation of the halo ketones from diazo ketones they are obtained free from isomers (cf. page 189). 

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