铜参与的碳硼烷锂盐与炔基锂的交叉偶联反应：“一锅法”合成C-炔基邻碳硼烷衍生物

doi:10.6023/cjoc201302007

有机化学 ›› 2013, Vol. 33 ›› Issue (08): 1774-1781.DOI: 10.6023/cjoc201302007 上一篇下一篇

研究论文

铜参与的碳硼烷锂盐与炔基锂的交叉偶联反应：“一锅法”合成C-炔基邻碳硼烷衍生物

卞德乾, 聂永, 苗金玲, 王亚峰, 张振伟

济南大学化学化工学院山东省氟化学化工材料重点实验室济南 250022

收稿日期:2013-02-03 修回日期:2013-03-10 发布日期:2013-04-09
通讯作者: 聂永 E-mail:chm_niey@ujn.edu.cn
基金资助:
国家自然科学基金(No. 20702020)及山东省自然科学基金(No. ZR2010BM020)资助项目.

Copper(I)-Mediated Cross-Coupling Reaction of Carboranyl-lithium with Alkynyllithium：One-Pot Synthesis of C-Alkynyl-o-carboranes

Bian Deqian, Nie Yong, Miao Jinling, Wang Yafeng, Zhang Zhenwei

School of Chemistry and Chemical Engineering, Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, University of Jinan, Jinan 250022

Received:2013-02-03 Revised:2013-03-10 Published:2013-04-09
Supported by:
Project supported by the National Natural Science Foundation of China (No. 20702020) and the Natural Science Foundation of Shandong Province (No. ZR2010BM020).

文章分享

1. 铜参与的碳硼烷锂盐与炔基锂的交叉偶联反应：“一锅法”合成C-炔基邻碳硼烷衍生物.PDF(1955KB)

摘要/Abstract

室温下氯化亚铜参与的邻碳硼烷双锂盐Li₂C₂B₁₀H₁₀的自偶联反应, 除了生成预期产物联邻碳硼烷(2), 还生成少量由邻碳硼烷锂盐和(为邻碳硼烷o-C₂B₁₀H₁₂锂化反应而引入的)过量丁基锂交叉偶联的产物1-丁基邻碳硼烷(4)和1,2-二丁基邻碳硼烷(5), 而氯化亚铜参与的邻碳硼烷、端炔、丁基锂的反应体系能够“一锅法”合成炔基邻碳硼烷(产率33～62%). 化合物5可由碳硼烷双锂盐与过量的1-溴丁烷反应获得(产率84.6%). 对化合物5与炔基碳硼烷衍生物通过核磁共振(¹H, ¹³C, ¹¹B)、红外光谱、质谱以及单晶X射线衍射(5)等手段进行了结构表征, 并对其可能的生成机理进行了探讨.

关键词: 碳硼烷, 簇状化合物, 有机锂, 炔烃, 交叉偶联

In the copper(I)-mediated homocoupling reaction of dilithio-o-carborane Li₂C₂B₁₀H₁₀at room temperature, the expected product 1,1'-bis(o-carborane) (2), the unexpected compounds 1-butyl-o-carborane (4) and 1,2-dibutyl-o-carborane (5) were obtained, the latter two being formed by the cross-coupling reaction of o-carboranyllithium with n-butyllithium (introduced for the lithiation of o-carborane C₂B₁₀H₁₂). Based on this finding, the CuCl-mediated one-pot synthesis of C-alkynyl-o-carborane derivatives (yield 33%～62%) involving o-carborane, terminal alkynes and n-butyllithium was developed. It was found that the product distribution varied with the amount of n-BuLi and CuCl utilized. Compound 5 was separately prepared in a good yield (84.6%) via the reaction of dilithio-o-carborane with excess 1-bromobutane at reflux for 23 h. The structural characterization of compound 5 and the C-alkynyl-o-carboranes were carried out by means of NMR, IR, MS and single-crystal X-ray diffraction (5). The possible mechanism for the formation of the cross-coupling products is also discussed.

Key words: carborane, cluster compounds, organolithium, alkynes, cross-coupling

引用此文

卞德乾, 聂永, 苗金玲, 王亚峰, 张振伟. 铜参与的碳硼烷锂盐与炔基锂的交叉偶联反应：“一锅法”合成C-炔基邻碳硼烷衍生物[J]. 有机化学, 2013, 33(08): 1774-1781.

Bian Deqian, Nie Yong, Miao Jinling, Wang Yafeng, Zhang Zhenwei. Copper(I)-Mediated Cross-Coupling Reaction of Carboranyl-lithium with Alkynyllithium：One-Pot Synthesis of C-Alkynyl-o-carboranes[J]. Chin. J. Org. Chem., 2013, 33(08): 1774-1781.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] (a) Liu, C.; Zhang, H.; Shi, W.; Lei, A.-W. Chem. Rev. 2011, 111, 1780.
(b) Shi, W.; Liu, C.; Lei, A.-W. Chem. Soc. Rev. 2011, 40, 2761.
(c) Li, B.-J.; Shi, Z.-J. Chem. Soc. Rev. 2012, 41, 5588.
[2] (a) Lipshutz, B. H.; Kayser, F.; Maullin, N. Tetrahedron Lett. 1994, 35, 815.
(b) Falck, J. R.; Mekonnen, B.; Yu, J.-R.; Lai, J.-Y. J. Am. Chem. Soc. 1996, 118, 6096.
(c) West, S. P.; Bisai, A.; Lim, A. D.; Narayan, R. R.; Sarpong, R. J. Am. Chem. Soc. 2009, 131, 11187.
(d) Surry, D. S.; Spring, D. R. Chem. Soc. Rev. 2006, 35, 218, and References therein.
(e) Jeffrey, J. L.; Bartlett, E. S.; Sarpong, R. Angew. Chem., Int. Ed. 2013, 52, 2194.
[3] For examples, see: (a) Walborsky, H. M.; Banks, R. B.; Banks, M. L. A.; Duraisamy, M. Organometallics 1982, 1, 667.
(b) Nagaki, A.; Uesugi, Y.; Tomida, Y.; Yoshida, J. Beilstein J. Org. Chem. 2011, 7, 1064.
(c) Fallon, T.; Willis, A. C.; Rae, A. D.; Paddon-Row, M. N.; Sherburn, M. S. Chem. Sci. 2012, 3, 2133.
[4] For examples, see: (a) Dubbaka, S. R.; Kienle, M.; Mayr, H.; Knochel, P. Angew. Chem., Int. Ed. 2007, 46, 9093.
(b) Cahiez, G.; Duplais, C.; Buendia, J. Angew. Chem., Int. Ed. 2009, 48, 6731.
(c) Dunst, C.; Kienle, M.; Knochel, P. Synthesis 2010, 2313.
(d) Wang, Z.-L.; Zhao, L.; Wang, M.-X. Chem. Commun. 2012, 48, 9418.
[5] Grimes, R. N. Carboranes, 2nd ed., Academic Press, Oxford, 2011.
[6] (a) Valliant, J. F.; Guenther, K. J.; King, A. S.; Morel, P.; Schaffer, P.; Sogbein, O. O.; Stephenson, K. A. Coord. Chem. Rev. 2002, 232, 173.
(b) Armstrong, A. F.; Valliant, J. F. Dalton Trans. 2007, 4240.
(c) Scholz, M.; Hey-Hawkins, E. Chem. Rev. 2011, 111, 7035.
(d) Issa, F.; Kassiou, M.; Rendina, L. M. Chem. Rev. 2011, 111, 5701.
[7] (a) Douvris, C.; Ozerov, O. V. Science 2008, 321, 1188.
(b) Reed, C. A. Chem. Commun. 2005, 1669.
(c) Grimes, R. N. Carboranes, 2nd ed., Academic Press, Oxford, 2011, Chapter 15.
(d) Bauer S.; Hey-Hawkins, E. in Boron Science, New Technologies and Applications, Ed.: Hosmane, N. S., CRC Press, Boca Raton, 2011, pp. 529～578.
[8] (a) Grimes, R. N. Carboranes, 2nd ed. Academic Press, Oxford, 2011, Chapter 17.
(b) Vöge, A.; Gabel, D. In Boron Science: New Technologies and Applications, Ed.: Hosmane, N. S., CRC Press, Boca Raton, 2011, pp. 295～318.
(c) Dash, B. P.; Satapathy, R.; Maguire, J. A.; Hosmane, N. S. New J. Chem. 2011, 35, 1955.
[9] (a) Dupont, J. A.; Hawthrone, M. F. J. Am. Chem. Soc. 1964, 86, 1643.
(b) Clegg, W.; Coult, R.; Fox, M. A.; Gill, W. R.; Hugh MacBride, J. A.; Wade, K. Polyhedron 1993, 12, 2711.
[10] (a). Zakharkin, L. I.; Kovderov, A. I.; Ol'shevskaya, V. A. Russ. Chem. Bull. 1986, 35, 1260.
(b) Zakharkin, L. I.; Kovredov, A. I. Russ. Chem. Bull. 1976, 25, 1593.
(c) Johnson, S. E.; Gomez, F. A.; Hawthorne, M. F.; Thorne, K. J.; MacKenzie, J. D. Eur. J. Solid State Inorg. Chem. 1992, 29, 113.
[11] Ren, S.; Xie, Z. Organometallics 2008, 27, 5167.
[12] Bian, D.-Q.; Nie, Y.; Miao, J.-L. J. Liaocheng Univ. (Nat. Sci. Ed.) 2012, 25(4), 30 (in Chinese).
(卞德乾, 聂永, 苗金玲, 聊城大学学报(自然科学版), 2012, 25(4), 30.)
[13] (a) Zakharkin, L. I.; Ponomarenko, A. A.; Okhlobystin, O. Y. Russ. Chem. Bull. 1964, 13, 2107.
(b) Gomez, F. A.; Hawthorne, M. F. J. Org. Chem. 1992, 57, 1384.
(c) Viñas, C.; Benakki, R.; Teixidor, F.; Casabo, J. Inorg. Chem. 1995, 34, 3844.
[14] Davidson, M. G.; Hibbert, T. G.; Howard, J. A. K.; Mackinnon, A.; Wade, K. Chem. Commun. 1996, 2285.
[15] Spokoyny, A. M.; Machan, C. W.; Clingerman, D. J.; Rosen, M. S.; Wiester, M. J.; Kennedy, R. D.; Stern, C. L.; Sarjeant, A. A.; Mirkin, C. A. Nat. Chem. 2011, 3, 590.
[16] Nador, F.; Fortunato, L.; Moglie, Y.; Vitale, C.; Radivoy, G. Synthesis 2009, 4027.
[17] Kuhn, P.; Alix, A.; Kumarraja, M.; Louis, B.; Pale, P.; Sommer, J. Eur. J. Org. Chem. 2009, 423.
[18] Alonso, F.; Melkonian, T.; Moglie, Y.; Yus, M. Eur. J. Org. Chem. 2011, 2524.
[19] Zheng, Q.; Hua, R.; Wan, Y. Appl. Organomet. Chem. 2010, 24, 314.
[20] Cahiez, G.; Duplais, C.; Buendia, J. Angew. Chem., Int. Ed. 2009, 48, 6731.
[21] Stuart, D. R.; Fagnou, K. Science 2007, 316, 1172.
[22] Han, G.-D. Synthetic Organic Chemistry, Petrochemical Industry Press, Beijing, 1977, p. 115 (in Chinese).
(韩广甸等编译, 有机制备化学, 石油化学工业出版社, 北京, 1977, 上卷, p. 115.)
[23] Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. J. Appl. Crystallogr. 2009, 42, 339.
[24] Sheldrick, G. M. Acta Crystallogr., Sect. A 2008, 64, 112.
[25] Batsanov, A. S.; Collings, J. C.; Fairlamb, I. J. S.; Holland, J. P.; Howard, J. A. K.; Lin, Z.; Marder, T. B.; Parsons, A. C.; Ward, R. M.; Zhu, J. J. Org. Chem. 2005, 70, 703.

铜参与的碳硼烷锂盐与炔基锂的交叉偶联反应：“一锅法”合成C-炔基邻碳硼烷衍生物

Copper(I)-Mediated Cross-Coupling Reaction of Carboranyl-lithium with Alkynyllithium：One-Pot Synthesis of C-Alkynyl-o-carboranes

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价

[1]	付雅彤, 孙超凡, 张丹, 金成国, 陆居有. 巢式-碳硼烷硼氢键官能化反应研究进展[J]. 有机化学, 2024, 44(2): 438-447.
[2]	童红恩, 郭宏宇, 周荣. 可见光促进惰性碳-氢键对羰基的加成反应进展[J]. 有机化学, 2024, 44(1): 54-69.
[3]	贝文峰, 潘健, 冉冬梅, 刘伊琳, 杨震, 冯若昆. 基于钴催化吲哚酰胺与二炔和单炔的[4+2]环化反应合成γ-咔啉酮[J]. 有机化学, 2023, 43(9): 3226-3238.
[4]	蒋宜欣, 唐伯孝, 毛海波, 陈雪霞, 俞洋杰, 全翠英, 徐昭阳, 石金慧, 刘益林. 水-聚乙二醇(PEG-200)中烯烃与碘代芳烃绿色可循环无负载偶联反应的研究[J]. 有机化学, 2023, 43(9): 3210-3215.
[5]	张素珍, 张文文, 杨慧, 顾庆, 游书力. 铑催化2-烯基苯酚与炔烃的对映体选择性螺环化反应[J]. 有机化学, 2023, 43(8): 2926-2933.
[6]	马佳敏, 李姣兄, 孟千森, 曾祥华. 炔烃的自由基砜基化反应研究进展[J]. 有机化学, 2023, 43(6): 2040-2052.
[7]	卢凯, 屈浩琦, 陈樨, 秋慧, 郑晶, 马猛涛. 无催化剂、无溶剂条件下炔烃和烯烃与儿茶酚硼烷的硼氢化反应[J]. 有机化学, 2023, 43(6): 2197-2205.
[8]	陈志豪, 范奇, 尹标林, 李清江, 王洪根. α-硼取代羰基类化合物的合成进展[J]. 有机化学, 2023, 43(5): 1706-1712.
[9]	李思达, 舒兴中, 吴立朋. 锆、钛介导的烯烃、炔烃硼氢化[J]. 有机化学, 2023, 43(5): 1751-1760.
[10]	高师泉, 刘闯军, 杨俊锋, 张俊良. 钴催化的烯烃和炔烃的电化学还原偶联反应[J]. 有机化学, 2023, 43(4): 1559-1565.
[11]	童宇星, 王子维, 刘奔, 徐耀威, 高颂, 唐向兵, 张兴华. 吲哚-3-硫醚类化合物的合成研究进展[J]. 有机化学, 2023, 43(4): 1310-1324.
[12]	贾海瑞, 邱早早. 过渡金属催化硼-氢键活化合成含硼-杂原子键邻碳硼烷衍生物的研究进展[J]. 有机化学, 2023, 43(3): 1045-1068.
[13]	刘婷婷, 胡宇才, 沈安. 亚胺配体协同氮杂环卡宾钯配合物催化碳碳偶联反应的作用机制[J]. 有机化学, 2023, 43(2): 622-628.
[14]	马彪, 章淼淼, 李占宇, 彭进松, 陈春霞. 无过渡金属催化的Suzuki-Type交叉偶联反应研究进展[J]. 有机化学, 2023, 43(2): 455-470.
[15]	刘鹏, 钟富明, 廖礼豪, 谭伟强, 赵晓丹. 炔烃参与的去芳构化反应构建螺环己二烯酮类化合物的研究进展[J]. 有机化学, 2023, 43(12): 4019-4035.