高效合成1,8-二芳基-1,3,5,7-共轭四炔的方法Efficient Synthesis of 1,8-diarylocta-1,3,5,7-tetraynes
李硕;毛凤;师瑶;王阳;石炜;
摘要(Abstract):
以金属催化的偶联反应为核心,发现了一种新的合成四炔的方法,首先从甲基丁炔醇出发,得到溴代甲基丁炔醇后,和末端炔烃发生Cadiot-Chodkiewicz偶联反应,得到共轭二炔.共轭二炔在碱性环境下脱去丙酮保护生成末端二炔烃后,在Ni和Cu共催化条件下发生Glaser-Hay氧化偶联反应,得到共轭四炔.该方法避免了贵金属催化剂的使用,反应条件温和,原料成本较低,产物易分离.
关键词(KeyWords): 共轭四炔;Cadiot-Chodkiewicz偶联反应;甲基丁炔醇;镍催化
基金项目(Foundation): 国家自然科学基金资助项目(21202050);; 湖北省自然科学基金资助项目(2014CFB930)
作者(Authors): 李硕;毛凤;师瑶;王阳;石炜;
参考文献(References):
- [1]Chalifoux W A,Ferguson M J,Tykwinski R R.Tris(biphenyl-4-yl)silyl-endcapped polyynes[J].Eur J Org Chem,2007(6):1001-1006.
- [2]马明,王建平,徐凌川.婆婆针化学成分的研究[J].中草药,2005,36(1):7-9.
- [3]张媛,木合布力·阿不力孜,李志远.金鸡菊属药用植物研究进展[J].中国中药杂志,2013,38(16):2633-2638.
- [4]Gung B W.Total synthesis of polyyne natural products[J].C R Chim,2009,12(3/4):489-505.
- [5]Ito A,Cui B,Chávez D,et al.Cytotoxic polyacetylenes from the twigs of ochanostachys amentacea[J].J Nat Prod,2001,64(2):246-248.
- [6]Chen G,Mahmud I,Dawe L N,et al.Synthesis and properties of conjugated oligoyne-centeredπ-extended tetrathiafulvalene analogues and related macromolecular systems[J].J Org Chem,2011,76(8):2701-2715.
- [7]Gulcur M,Moreno-Garcia P,Zhao X,et al.The synthesis of functionalised diaryltetraynes and their transport properties in single-molecule junctions[J].Chem-Eur J,2014,20(16):4653-4660.
- [8]Li Y,Winkel R W,Weisbach N,et al.Photophysics of platinum tetrayne oligomers:delocalization of triplet exciton[J].J Phys Chem A,2014,118(45):10333-10339.
- [9]Metay E,Hu Q,Negishi E I.Highly efficient and selective synthesis of conjugated triynes and higher oligoynes of biological and materials chemical interest via palladium-catalyzed alkynyl-alkenyl coupling[J].Org Lett,2006,8(25):5773-5776.
- [10]范永发,余从煊,刘敬镛,等.一种全新的四炔类非线性光学材料[J].北京理工大学学报,1994,14(S1):30.
- [11]Negishi EI,Hata M,Xu C.A strictly“pair”-selective synthesis of conjugated diynes via Pd-catalyzed cross coupling of1,3-diynylzincs:a superior alternative to the Cadiot-Chodkiewicz reaction[J].Org Lett,2000,2(23):3687-3689.
- [12]Chalifoux W A,Tykwinski R R.Synthesis of polyynes to model the sp-carbon allotrope carbyne[J].Nat Chem,2010,2(11):967-971.
- [13]Tykwinski R R,Chalifoux W,Eisler S,et al.Toward carbyne:synthesis and stability of really long polyynes[J].Pure Appl Chem,2010,82(4):891-904.
- [14]Shi W,Lei A.1,3-Diyne chemistry:synthesis and derivations[J].Tetrahedron Lett,2014,55(17):2763-2772.
- [15]Kato S I,Takahashi N,Nakamura Y.Hexadecadehydrodibenzo[20]-,tetracosadehydrotribenzo[30]-,and dotriacontadehydrotetrabenzo[40]annulenes:syntheses,characterizations,electronic properties,and self-associations[J].J Org Chem,2013,78(15):7658-7663.
- [16]Yin W,He C,Chen M,et al.Nickel-catalyzed oxidative coupling reactions of two different terminal alkynes using O2as the oxidant at room temperature:facile syntheses of unsymmetric 1,3-diynes[J].Org Lett,2009,11(3):709-712.