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제107회 대한화학회 학술발표회, 총회 및 기기전시회 안내
One-Pot Synthesis of 1,4-Disubstituted 1,3-Diynes via Pd-Catalyzed Decarboxylative Coupling of Propiolic Acids
2011년 2월 18일 15시 01분 35초
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울산대학교 화학과, Korea
Conjugated 1,3-diynes are very crucial materials in the fields of chemistry, biology and material science, because they have been used in the preparation of natural products, organic and inorganic composites, pharmaceuticals, and π-conjugated polymers as well as the molecular recognition process. Traditional method for the construction of symmetrical or unsymmetrical 1,3-diynes is oxidative homocoupling reactions of terminal alkynes, reported by Glaser, via the treatment of Cu(I) salt in the presence of aqueous ammonia followed by air oxidation. Later related modified methods to improve the disadvantage of the original reaction condition were developed by Eglinton, Hay, Chodkiewicz-Cadiot, and Yu. Pioneering work for the preparation of symmetrical 1,3-diynes using palladium catalysis was reported by Rossi et al. in 1985. Recently, Lei et al. demonstrated new process for the construction of unsymmetrical 1,3-diynes, which includes Ni-catalyzed oxidative coupling of two different terminal alkynes with a high loading of one alkyne partner. However, these methodologies present intrinsic drawbacks, namely the need for prefunctionalization of both coupling partners. For examples, in the case of homocoupling of terminal alkynes, the preparation of terminal alkynes were often required, i.e. via Corey-Fuchs reaction using aldehydes, Fritsch-Buttenberg-Wiechell rearrangement of vinyl bromides, Seyferyth-Gilbert homologation using aldehydes, and Sonogashira reaction between haloarenes and metal (Si or Sn)-substituted acetylenes followed by reductive hydrogenation. Moreover, the methods for the synthesis of unsymmetrical 1,3-diynes have required the prefunctionalization to prepare haloalkynes or propiolic acids as well as terminal alkynes. The multi-step syntheses required for the preparation of such substrates can pose additional barriers to their use. Therefore, it is highly desirable to develop more efficient methodologies saving synthetic steps and avoiding waste formation for synthesizing conjugate 1,3-diynes. Herein, we demonstrate direct synthesis of symmetrical 1,4-disubstituted 1,3-diynes from iodoarenes and propiolic acid via Sonogashira reaction followed by Pd-catalyzed decarboxylative homocoupling. Furthermore, one-pot synthesis of unsymmetrical 1,4-disubstituted 1,3-diynes by cross-coupling of two different 3-substituted propiolic acids is described.
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