Synthesis of Tetra(BINOL) Substituted Spirobifluorenes

Abstract

A series of tetra(BINOL) substituted spirobifluorenes (1, 12-15) has been prepared via fourfold Sonogashira cross-coupling reaction from 2,2′,7,7′-tetraiodospirobifluorene (3) and 2,2′-bis(methoxymethoxy)-3-ethynyl-1,1′-binaphthyl (10) or 2,2′-bis(methoxymethoxy)-3-ethynyl-3′-[(trimethylsilyl)ethynyl]-1,1′-binaphthyl (11), respectively. Whereas the deprotection of the readily available fully methoxymethyl ether protected precursors 12 and 13 proved to be difficult in the case of the sterically shielded spirobifluorenes 14, 15, not further substituted tetra(BINOL) 1 could be obtained in good yield after acidic hydrolysis. This chiral spirobifluorene closely reassembles the structure of copper(I) or silver(I) complexes of a bis(BINOL) substituted 2,2-bipyridine (2) and can also form two clefts with the BINOL groups orientated in a fashion potentially useful for the co-operative molecular recognition of chiral substrates.

Key words

cross-coupling reactions - palladium - BINOL - spiro compounds - supramolecular chemistry

References

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