Pd催化苯乙烯脱氢氧化偶联研究
Pd(II)-Catalyzed Dehydrogenative Oxidative Coupling of Terminal Alkene of Styrene

作者: 龚 颖 , 王光祖 :合肥工业大学医学工程学院,安徽 合肥;

关键词: 苯乙烯共轭二烯烃脱氢Heck反应Styrene Conjugated Dienes Dehydrogenative Heck Reaction

摘要:
我们对未活化的苯乙烯末端烯烃进行了脱氢Heck反应的研究,运用Pd(acac)2做催化剂,Cu(OAc)2作氧化剂,并添加少量AgF,乙酸乙酯作溶剂,在100℃下反应24 h,苯乙烯直接脱氢得到1,4-二苯基-1,3-丁二烯,具有共轭结构,能作为许多有价值化合物的中间体,具有潜在的应用价值,我们还对该反应提出了一个可能的机理。

Abstract: The work about dehydrogenative Heck reaction of unactivated terminal alkene of styrene was studied. Using Pd(acac)2 as catalyst, Cu(OAc)2 as oxidant, EtOAc as solvent, and adding some AgF, at 100˚C for 24 h, styrene was directly dehydrogenized to generate 1,4-dipheny-1,3-butadiene with conjugated construction which can be intermediate of many value compounds, so this reaction has potential value. A plausible mechanism was proposed.

文章引用: 龚 颖 , 王光祖 (2015) Pd催化苯乙烯脱氢氧化偶联研究。 有机化学研究, 3, 91-96. doi: 10.12677/JOCR.2015.32013

参考文献

[1] Tamao, K. and Miyaura, N. (2002) Introduction to cross-coupling reactions. Topics in Current Chemistry, 219, 1-9.

[2] Yu, D.-G., Li, B.-J. and Shi, Z.-J. (2010) Exploration of new C-O electrophiles in cross-coupling reactions. Accounts of Chemical Researh, 43, 1486-1495.

[3] Gligorich, K.M. and Sigman, M.S. (2009) Recent advancements and challenges of palladiumII-catalyzed oxidation reactions with molecular oxygen as the sole oxidant. Chemical Communications, 26, 3854-3867.

[4] Nicolaou, K.C., Daines, R.A., Ogawa, Y. and Chakraborty, T.K.J. (1988) Total synthesis of amphotericin B. 3. The final stages. Journal of the American Chemical Society, 110, 4696-4705.

[5] Negishi, E., Huang, Z., Wang, G., Mohan, S., Wang, C. and Hattori, H. (2008) Recent advances in efficient and selective synthesis of di-, tri-, and tetrasubstituted alkenes via Pd-catalyzed alkenylation-carbonyl olefination synergy. Accounts of Chemical Researh, 41, 1474-1485.

[6] Dong, D.J., Li, H.H. and Tian, S.K.J. (2010) A highly tunable stereoselective olefination of semistabilized triphenylphosphonium ylides with n-sulfonyl imines. Journal of the American Chemical Society, 132, 5018.

[7] Wadsworth, W.S. and Emmons Jr, W.D. (1961) The utility of phosphonate carbanions in olefin synthesis. Journal of the American Chemical Society, 83, 1733-1738.

[8] Julia, M. and Paris, J.M. (1973) Syntheses a l’aide de sulfones v(+)-methode de synthese generale de doubles liaisons. Tetrahedron Letters, 14, 4833-4836.

[9] Peterson, D.J.J. (1968) Carbonyl olefination reaction using silyl-substituted organometallic compounds. Journal of Organic Chemistry, 33, 780-784.

[10] Stille, J.K. (1986) The palladium-catalyzed cross-coupling reactions of organotin reagents with organic electrophiles [New Synthetic Methods (58)]. Angewandte Chemie International Edition in English, 25, 508-524.

[11] Le Bras, J. and Muzart, J. (2011) Intermolecular dehydrogenative heck reactions. Journal of Chemical Reviews, 111, 1170-1214.

[12] Negishi, E. (2007) Transition metal-catalyzed organometallic reactions that have revolutionized organic synthesis. Bulletin of the Chemical Society of Japan, 80, 233-257.

分享
Top