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제116회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Phosphoryl Alkylindiums and Their Synthetic Application to Arylalkyl Phosphonates via Palladium-Catalyzed Cross-Coupling Reactions

2015년 8월 27일 15시 55분 51초
ORGN.P-377 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
10월 15일 (목요일) 11:00~12:30
저자 및
김상혁, 신서현, 이필호*
강원대학교 화학과, Korea
Organophosphonate is an essential functional group in synthetic as well as biological chemistry. In synthetic chemistry, it is a starting material for the preparation of alkenes via the Horner-Wadsworth-Emmons reaction. In biological chemistry, their distinctive structure and polarity provide them a significant function in pharmaceuticals and agrochemicals. Therefore, a wide range of synthetic intermediates and precursors and biologically active compounds require introduction of a phosphonate group to the molecule. To date, the most conventional approaches for the formation of the P-C (sp3) bond are the Michaelis-Arbuzov and Michaelis-Becker reactions. Despite its prevalence, the trivalent phosphorus compounds employed in the Michaelis-Arbuzov reaction have normally low stability and effuse a repulsive odor. The Michaelis-Becker reaction occasionally needs long reaction times and a strong base. Thus, we envisioned that if organometallic reagents having a phosphonate group can be successfully prepared, it will be an efficient synthetic method of functionalized organophosphonates via C-C bond-forming reaction. We have developed in situ preparation of phosphoryl alkylindiums from the direct insertion of indium with bromoalkyl phosphonates in the presence of CuCl. The Pd-catalyzed cross-coupling reaction of the phosphoryl alkylindium reagents with a number of aryl iodides, bromides, and triflates and vinyl bromide proceeded smoothly to provide the functionalized arylalkyl phosphonates in good to excellent yields. A wide range of functional groups, including ester, ketone, aldehyde, nitrile, nitro, trifluoromethyl, chloride, methoxy, hydroxy, and amino, are tolerable in the cross-coupling reactions. Upon increasing the chain length between the bromide and the phosphoryl group, the directing effect by the phosphoryl group is observed.