Additions of Lithiated Alkoxyallenes to Phthalimide: A New Synthesis of Pyrroloisoindolones and an Unusual Olefination Reaction

Abstract

Addition of an excess of lithiated alkoxyallenes to phthalimide­ 5 provided the expected primary adducts 7a-c, which could be cyclized via their oxygen moiety to furnish spirofuran derivatives 8a-c. After selective protection of the hydroxyl function of 7a-c the resulting siloxy derivatives 11a-c were transformed by gold(III) catalysis into pyrroloisoindolones 13a-c in moderate yields. This establishes a new approach to this class of heterocycles in a [3+2] fashion with the alkoxyallenes as functionalized C-3 unit and phthalimide 5 providing the CN moiety. Treatment of primary adducts 7a-c with aqueous sulfuric acid surprisingly led to compounds 14a-c in good yields. The constitution of these products was proved by an X-ray analysis of derivative 15a. Aqueous hydrochloric acid converted 7a into a similar product 17 containing a chlorine substituent. These reactions can be considered as olefination reactions of phthalimide.

Key words

allenes - lithium - imide - pyrroloisoindolones - gold catalysis

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19

Crystallographic data for 15a can be obtained from Cambridge Crystallographic Data Centre, CCDC reference number: 286363.