1,2-联烯基酮的合成与反应

Synthesis and Reaction of 1,2 - Allenyl Ketones

1,2-联烯基酮可以通过2-丙炔基酮异构化反应,相应有机金属试剂中间体与酯、酸氢或酰胺的反应,[2,3]或[3,3]迁移反应,Wittig反应,消除反应,2,3-联烯醇氧化等方法合成。由于联烯酮上含有吸电子基团羰基,它可发生亲核加成、环加成、环化反应。

Recently, much attention has been paid to the chemistry of 1,2- allenyl ketones, due to their high and unique reactivity. In this paper we wish to review the synthesis and reaction of 1,2- allenyl ketones. 1,2- Allenyl ketones can be synthesized by the following methods: (1) Oxidation of homopropargylic alcohols to the propargyl ketones, followed by the isomerization; (2) Reaction of appropriate organornetallic reagents with esters, acyl chlorides or amides; (3) Oxidation of 2,3 - allenyl alcohols; (4) [2,3] or [3,3] Rearrangement of the corresponding functionalized alkynes; (5) Reaction of the corresponding Wittig reagents with acyl chloride or ketenes; (6) Elimination of B - halogen B,r - or a, B - unsaturated enones; and others. 1,2- Allenyl ketones can participate nucleophilic addition, cycloaddition and cyclization reactions. (1) The 1,4- nucleophilic reaction with 1,2- allenyl ketones selectively afforded B, r - or a, B - unsaturated enones. Nucleophiles could be ROH, RSH, RR'NH, HX. (2) Reaction of LiAH4, DIBAL or organomagnesium with the carbonyl groups of 1,2- allenyl ketones afforded the 1,2- addition products allenyl alcohols. (3) The cycloaddition of 1,2 - allenyl ketones with 1,3- butadienes, 1,3- cyclopentadienes, and furans to provide efficient routes to six - membered products. The 1,3- dipolar cycloaddition of 1,2- allenyl ketones with dia-zomethane afforded five - membered heterocyclic compounds. (4) 1,2- Allenyl ketones can be thermally rearranged to furans. The cyclization reaction can also be catalyzed by silver(I) and Pd(II). (5) Allenyl ketones bearing an aryl group are prone to proceed a new intramolecular electrophilic substitution reaction using BF3·OEt2 or Hg(ClO4)2 as the catalyst.