Heteroatom Nucleophile Induced C–C Fragmentations to Access Functionalized Allenes

Abstract

The rich structural and reactivity profile of allenes render them versatile synthetic intermediates. However, application of allenes in organic chemistry is often attenuated by inconvenient methods of preparation. Herein we present an operationally simple route to functionalized allenes from vinyl triflate precursors through a Grob-type fragmentation induced by heteroatom nucleophiles such as water, alcohols, thiols or amines. The fragmentation occurs under mild conditions and is well suited for one-pot or domino processes allowing access to a range of synthetically useful intermediates.

Teaching Enantioselectivity to C–H Bond Functionalizations: Initial Steps of a Rather Long Shot

“…After the successful initial an interesting and synthetically useful solvent-induced Grob fragmentation, which was recently highlighted in CHIMIA as an SCS-Poster award account. [22] As second substrate class, we then turned our attention towards aniline derivatives 12 previously shown as viable for achiral C-H functionalization. This is an appealing substrate class which is conformationally more restricted and gives rise to the pharmacologically important indoline scaffold 13 (Scheme 8).…”