Benzylmanganese Complexes의 반응 = Reaction of ??-Benzylmanganese Complexes

국문 초록 (Abstract)

(?-pentamethylcyclohexadienyl-exo-ene)manganesedicarbonyl triphenyl- 과 trialkylphosphite ??가 자연 반응되어 각각 diphenyl-과 dialkylphosphonate complexes로 변하는 것을 확인하였다. 이 반응에서 triphenylphosphite derivatives가 benzyne을 생성하는 것을 diphenylene을 검출함으로써 알아냈고, trialkylphosphite complexes는 alkylidene을 생성하는 것을 olefins을 사용한 trapping experiments를 통하여 확인할 수 있었다. Deuterium을 포함한 complexes 2b와 2d가 각각 phosphonate complexes 3b와 3d로 변하는 것을 관찰함으로써 이 반응의 hydrogen의 source가 이 화합물의 trialkyl-이나 triphenylphosphitc ligand임을 증명하였다. 역시 deuterium을 포함한 complex 2f를 사용하여 trialkylphosphite complexes의 반응의 경우 α-proton의 elimination이 유일한 반응경로임을 증명하였다. 여기 보고된 반응들은 유기합성에서 중요한 역할을 하는 것으로 알려진 benzyne과 alkylidenes의 새로운 source로서의 가능성을 가지고 있다.

국문 초록 (Abstract)

(?-pentamethylcyclohexadienyl-exo-ene)manganesedicarbonyl triphenyl- 과 trialkylphosphite ?? have been observed to spontaneously decompose to give the corresponding diphenyl- or dialkylphosphonate complexes. In these reactions, the triphenylphosphite derivatives produced benzyne as confirmed by the detection of diphenylene and the trialkylphosphite complexes eliminated the element of alkylidene as evidenced by trapping experiments with olefins. The conversion of the deuterium labeled complexes 2b and 2d to the corresoponding phosphonate complexes 3b and 3d establishes that the source of the protons in these decompositions is the triakyl- or triphenylphosphite ligand of those complexes. Using the deuterium labeled complex 2f, it has been demonstrated that elimination of an α-proton is the exclusive pathway in the case of the decomposition of trialkylphosphite complexes. The reactions reported here have the potential of establishing a new source of benzyne and alkylidenes which are known to play important roles in organic syntheses.