백금 핀서 화합물의 합성 및 Silylcyanation 촉매반응에 대한 응용

김윤태; 윤명식; Yun Tae Kim; Myeong Sik Yoon

Applied Chemistry for Engineering, Vol.27, No.4, 366-370, August, 2016

DOI10.14478/ace.2016.1030 Export Citation

백금 핀서 화합물의 합성 및 Silylcyanation 촉매반응에 대한 응용

Synthesis of a Platinum-Pincer Complex and Application to Catalytic Silylcyanation

김윤태¹, 윤명식^{1, 2, †}

¹호서대학교 제약공학과
²호서대학교 기초과학연구소

Yun Tae Kim¹, and Myeong Sik Yoon^{1, 2, †}

¹Department of Pharmaceutical Engineering, Hoseo University, 20, Hoseo-ro 79, Baebang, Asan, Chungcheongnam-do 31499, Korea
²The Research Institute for Basic Sciences, Hoseo University, 20 Hoseo-ro 79, Baebang, Asan, Chungcheongnam-do 31499, Korea

E-mail:

초록

본 연구에서는 1,3-bis(2-pyridyloxy)benzene과 K2PtCl4를 이용하여 백금을 중심으로 2개의 6원환을 이루는 백금 핀서화합물을 합성하였다. NMR과 X-ray를 이용하여 구조를 규명하였고 백금원자를 중심으로 이루는 6원환 구조는 angle strain을 감소시켜 안정한 화합물을 형성하였다. 이 화합물을 알데하이드와 이민의 silylcyanation 반응에 적용하여 본 결과 수율 99%까지 나타내는 효과적인 촉매작용을 보여주었다.

A platinum(II) pincer complex composed of two six-membered fused metallacycles was directly synthesized using 1,3-bis(2-pyridyloxy)benzene and K2PtCl4. The structure of the complex was elucidated via NMR and X-ray crystallography analysis. The stable complex was formed due to the six-membered fused cycle structure around the Pt(II) center which reduced the bond angle strain. The complex was applied to the silylcyanation reaction of aldehydes and imines and showed an efficient catalytic activity with 99% yield.

Keywords:platinum;x-ray structure;catalyst;silylcyanation;pincer complex

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[2] Rietveld MPH, Grove DM, Koten GV, New J. Chem., 21, 751 (1997)

[3] Albrecht M, Koten GV, Angew. Chem.-Int. Edit., 40, 3751 (2001)

[4] Botchway SW, Charnley M, Haycock JW, Parker AW, Rochester DL, Weinstein JA, Williams JAG, Proc. Natl. Acad. Sci. USA, 105, 16071 (2008)

[5] To WP, Chan KT, Tong GSM, Ma C, Kwok WM, Guan X, Low KH, Che CM, Angew. Chem.-Int. Edit., 52, 6648 (2013)

[6] Zhang H, Zhang BG, Li YJ, Sun WF, Inorg. Chem., 48(8), 3617 (2009)

[7] Soro B, Stoccoro S, Minghetti G, Zucca A, Cinellu MA, Gladiali S, Manassero M, Sansoni M, Organometallics, 24, 53 (2005)

[8] Cardenas DJ, Echavarren AM, Organometallics, 18, 3337 (1999)

[9] Slagt MQ, Mguez GR, Grutters MMP, Gebbink RJMK, Klopper W, Jenneskens LW, Lutz M, Spek AL, Koten GV, Chem.-Eur. J., 10, 1331 (2004)

[10] Kuil LAVD, Grove DM, Gossage RA, Zwikker JW, Jenneskens LW, Drenth W, Koten GV, Organometallics, 16, 4985 (1997)

[11] Selander N, Szab JK, Chem. Rev., 111, 2048 (2010)

[12] Geest DJD, Keefe BJO, Steel PJ, J. Organomet. Chem., 579, 97 (1999)

[13] Keefe BJO, Steel PJ, Organometallics, 22, 1281 (2003)

[14] Canty AJ, Minchin NJ, Skelton BW, White AH, J. Chem. Soc.-Dalton Trans., 1987(6), 1477 (1987)

[15] Yoon MS, Ramesh R, Kim J, Ryu D, Ahn KH, J. Organomet. Chem., 691, 5927 (2006)

[16] Fossey JS, Richards CJ, Tetrahedron Lett., 44, 8773 (2003)

[17] Yoon MS, Ryu D, Kim J, Ahn KH, Organometallics, 25, 2409 (2006)

[18] Chiu BKW, Lam MHW, Lee DYK, Wong WY, J. Organomet. Chem., 689, 2888 (2004)

[19] Groutas WC, Felker D, Synthesis, 1980(11), 861 (1980)

[20] Lidy W, Sundermeyer W, Chem. Ber., 106, 587 (1973)

[21] Noyori R, Murata S, Suzuki M, Tetrahedron, 37, 3899 (1981)

[22] Vougioukas AE, Kagan HB, Tetrahedron Lett., 28, 5513 (1987)

[23] Vale JA, Faustino WM, Menezes PH, de Sa GF, J. Braz. Chem. Soc., 17, 829 (2006)

[24] Brunel JM, Holmes IP, Angew. Chem.-Int. Edit., 43, 2752 (2004)

[25] North M, Tetrahedron: Asymmetry, 14, 147 (2003)

[26] Khan NH, Kureshy RI, Abdi SHR, Agrawal S, Jasra RV, Coord. Chem. Rev., 252, 593 (2008)

[27] Hayashi M, Miyamoto Y, Inoue T, J. Org. Chem., 58, 1515 (1993)

[28] Jiang Y, Zhou X, Hu W, Wu L, Mi A, Tetrahedron: Asymmetry, 6, 405 (1995)

[29] Jiang Y, Gong L, Feng X, Hu W, Pan W, Li Z, Mi A, Tetrahedron, 53, 14327 (1997)

[30] Pitchaimani P, Lo KM, Elango KP, Polyhedron, 93, 8 (2015)

[31] Xia J, Xu JN, Fan Y, Song TY, Wang L, Zheng JF, Inorg. Chem., 53(19), 10024 (2014)

[32] Reddy VVR, Saritha B, Ramu R, Varala R, Jayashree A, Asian. J. Chem., 26, 7439 (2014)

[33] Karmakar B, Banerji J, Tetrahedron Lett., 51, 2748 (2010)

[34] Kantam ML, Mahendar K, Sreedhar B, Choudary BM, Tetrahedron, 64, 3351 (2008)

[35] Hou YL, Sun RWY, Zhou XP, Wang JH, Li DA, Chem. Commun., 50, 2295 (2014)