1,3-diketones displacement reactions

Both overt carbanions and organometallic compounds, such as Grignard reagents, are powerful nucleophiles as we have seen in their addition reactions with C=0 (p. 221 et seq.) they tend therefore to promote an SN2 pathway in their displacement reactions. Particularly useful carbanions, in preparative terms, are those derived from CH2(C02Et)2, (3-ketoesters, l,3-( 3-)diketones, e.g. (55), a-cyanoesters, nitroalkanes, etc.—the so-called reactive methylenes ... 

Other workers have concurrently developed the extensive acid-base chemistry of palladium and platinum /l-diketonates.44 452 Sequential displacement reactions also occur with Pt(CF3COCHC-OCF3)2, Pt(CF3COCHCOMe)2 and Pd(CF3COCHCOMe)2. Pdtetrakis(aniline)2+ diketonates are... 

Active methylene or methine compounds, to which two EWGs such as carbonyl, alko.xycarbonyl, formyl, cyano, nitro, and sulfonyl groups are attached, react with butadiene smoothly and their acidic hydrogens are displaced with the 2,7-octadienyl group to give mono- and disubstituted compounds[59]. 3-Substituted 1,7-octadienes are obtained as minor products. The reaction is earned out with a /3-keto ester, /9-diketone, malonate, Q-formyl ketones, a-cyano and Q-nitro esters, cya noacetamide, and phenylsulfonylacetate. Di(octadienyl)malonate (61) obtained by this reaction is converted into an... 

Yosikoshi reported the synthesis of furan derivatives by the reaction of 1,3-diketones with nitroalkenes, in which the Michael addition of the anions of 1,3-diketones and the subsequent intramolecular displacement of the nitro group by enolate oxygen are involved as key steps (Eq. 7.40).42... 

Ketols can also be formed enzymatically by cleavage of an aldehyde (step a, Fig. 14-3) followed by condensation with a second aldehyde (step c, in reverse). An enzyme utilizing these steps is transketolase (Eq. 17-15),132b which is essential in the pentose phosphate pathways of metabolism and in photosynthesis. a-Diketones can be cleaved (step d) to a carboxylic acid plus active aldehyde, which can react either via a or c in reverse. These and other combinations of steps are often observed as side reactions of such enzymes as pyruvate decarboxylase. A related thiamin-dependent reaction is that of pyruvate and acetyl-CoA to give the a-diketone, diacetyl, CH3COCOCH3.133 The reaction can be viewed as a displacement of the CoA anion from acetyl-CoA by attack of thiamin-bound active acetaldehyde derived from pyruvate (reverse of step d, Fig. 14-3 with release of CoA). 

Many metal / -diketonates are coordinatively unsaturated and reactions with Lewis bases to form complexes are a pervasive feature of their chemistry.14 In previous sections, base cleavage of M—O—M bridge bonds in oligomeric acetylacetonates and formation of hydrated lanthanide dike-tonates having high, odd coordination numbers have been noted. Mechanistically, acid-base complexes are quite likely to be involved in hydrolysis, displacement and ort/zo-metallation reactions, albeit that the interactions may be weak. 

The reaction, of metal carbonyls with 1,3-diketones generally results in a complete displacement of carbon monoxide accompanied by oxidation of the metal to yield 1,3-diketonato complexes. For example, iron pentacarbonyl, chromium hexa-carbonyl, and molybdenum hexacarbonyl afford FefCgHjOOs,1 Cr(CsHr02)8,2 and Mo(CgH702)s,2,s respectively, when allowed to react with 2,4-pentanedione. 

---