Cyclopropanation of enantiopure metal alkenyl carbenes with 2-methoxyfuran:: A practical route to carboxycyclopropylglycine precursors

We have examined the reactivity of enantiopure alkenyl Fischer carbene complexes 1, readily available from the chiral pool, with 2-methoxyfuran 4. In this reaction, polyfunction-alised cyclopropylcarbenes 5 are obtained under very mild conditions and with high selectivity, the major stereoisomer being isolated in an enantiopure form. The reaction involves the conjugate nucleophilic addition of 2-methoxyfuran 4 to the carbene complexes 1 followed by ring closure of the resulting zwitterionic intermediate species. The oxidation of the carbene 5a results in the formation of the enantiopure cyclopropane diester 6. Further elaboration of the cyclopropane 6 allows for an efficient enantioselective access to alcohols or diols 7-9 as well as to cyclopropanecarbaldehydes 10-12. The protocol described herein provides a very simple entry to interesting enantiopure precursors of carboxycyclopropylglycine derivatives from readily available starting materials. In order to test this potential as carboxycyclopropylglycine precursors, the aminocyanation of the cyclopropanecarbaldehyde 10 was undertaken and the alpha-amino-cyano derivative 13 was isolated as a single diastereosiomer.