A study of microwave-induced and standard thermal Overman rearrangement of selected allylic trichloroacetimidates 1a-1f, 6-8 to the corresponding acetamides 2a-2f, 9-11 is reported. The microwave-assisted rearrangement of trifluoroacetimidate 13 is also described. Using this methodology, an efficient access to versatile allylic trihaloacetamides building synthons was established.

1. Scheby-Buch.-Arch. f. Ophthal., p. 265, 1871. 2. Moll.-Centralbl. f. prakt Augenheilk, p. 2, 1896. 3. Weber.-Virchow's Arch., Vol. XXV, p. 114b, and Vol. XXVIII, p. 489, 1863. % 4. Schmidt-Rimpler.-Klin. Wochenschr., p. 92, 1884. Berlin. 5. Aubertin.-Rev. Gen. d'Ophtal., p. 280, 1933. 6. Lohmann.-Beticht iuber d. Vers. d. Ophthal. Gesellsch., p. 264, 1908. Heidelberg. 7. Stephenson.The Ophth...

The modular polyketide synthase leading to the formation of the erythromycin aglycone 6-deoxyerythronolide B (6dEB) in Saccharopolyspora erythraea is one of the best studied, especially regarding stereochemistry. Biosynthesis proceeds by Claisen condensation with inversion of configuration to give a 2R methyl centre. However, the methyl stereochemistry of 6dEB implies that two epimerisation ste...

Here we describe a 5-step sequence to prepare the AB enone 1, the key precursor to fully synthetic tetracyclines, that begins with a diastereoselective Michael-Claisen coupling of two simple starting materials, a cyclohexenone (compound 2 or, in a refinement, a substituted variant, vide infra) and the isoxazole ester 3. This advance defines an 8-step linear sequence to 6-deoxytetracycline antib...

A stereoselective synthesis of (+)-physoperuvine, a tropane alkaloid from Physalis peruviana Linne has been developed using a one-pot tandem aza-Claisen rearrangement and ring closing metathesis reaction to form the key amino-substituted cycloheptene ring.

The first total synthesis of the proposed structure of astakolactin, a sesterterpene metabolite isolated from the marine sponge Cacospongia scalaris, has been achieved, mainly featuring Johnson-Claisen rearrangement, asymmetric Mukaiyama aldol reaction and MNBA-mediated lactonization.