使用 錸（I）和釕（II）催化劑於N-吡啶基/ N-Pyrimidylindole和N-Methoxybenzamide系列物的進行具區域和立體選擇性的C（sp2）- H化學鍵官能基化；同時使用不具金屬和沒有氧化劑的氧化劑來進行分子內的C–N化學鍵官能基化

“Rhenium (I) & Ruthenium (II) Catalyst for the Regio- and Stereoselective C(sp2)−H bond functionalization of N- Pyridyl-/ N- Pyrimidylindole and N-Methoxybenzamide and Metal and Oxidant free intramolecular C-N bond formation using Oxazolineamide”

薩拉特(Sundaramoorthi Sarathkumar)

指導教授 ： 姚清發

國立臺灣師範大學/理學院/化學系/博士(2021年)

https://doi.org/10.6345/NTNU202100420

摘要

此論文的內容共分為四個章節，分別為A、B 、 C和D。
[A] 章節的內容涵蓋四個部分。第一部分是C–H化學鍵進行官能基化的介紹；第二部分為應用錸（I）催化劑在各類型的C–H化學鍵進行官能基化反應的介紹及其分析；第三部分是介紹釕（II）催化劑來催化C–H化學鍵進行官能基化反應的探討；而最後一部分則是介紹使用各類型的過渡金屬催化劑來合成喹唑啉酮。
[B] 章節包含幾個部分，主要是集中於屬於水溶性的 Re（I）催化劑的介紹。在溫和的條件以及使用水作為溶劑時，上述催化劑可應用於N-吡啶基/ N-嘧啶基吲哚系列物來進行具有區域和立體選擇性的碳（sp2）–氫烯基化反應，以及應用於N-嘧啶基苯胺衍生物與N-酰胺可進行N–H烯基化的反應。當使用水作為溶劑時，此催化系統具有可回收性的特性，同時也對反應機構以及動力學研究做了詳細的討論。最後是對於[Re（CO）3（H2O）3] Br催化劑的介紹及討論。
[C] 章節是介紹在微波的條件下，釕（II）世紀可催化炔基硫烷對N-甲氧基苯甲酰胺的C–H / N–O進行活化作用。這部分同時對反應機構進行探討以及其數據進行分析。
[D] 章節描述了在不使用金屬和氧化劑的條件下，噁唑啉酰胺可進行分子內C–N化學鍵的官能基化反應。本章還同時也對反應機構進行探討以及其數據進行分析。

關鍵字

錸（I）和釕（II）催化劑 ； C–H化學鍵的官能基化 ； 水 ； N-吡啶基-/ N-嘧啶基吲哚 ； 3-（苯基乙炔基）噁唑烷丁-2-酮 ； N-甲氧基苯甲酰胺 ； 炔基硫烷 ； 醋酸銫 ； 新戊酸鈉 ； 無金屬和氧化劑 ； 對甲苯磺酸一水合物 ； 噁唑啉酰胺 ； 喹唑啉酮

並列摘要

The contents of this dissertation are divided into four chapters (A, B, C & D).
Chapter [A] is subdivided into four parts. Part one is the introduction of C-H bond functionalization. Likewise, part two is focusing on a detailed introduction and depth analysis of various types of C-H bond functionalization reaction using a rhenium (I) catalyst. Then part three is a feature introduction and numerous categories of C-H bond functionalization reaction using a Ruthenium (II) catalyst. Moreover, the final part is the introduction and synthesis of quinazolinones using various types of transition metal catalysts.
Chapter [B] contains several parts as mainly focus on “a water-soluble rhenium (I)-catalyst for the regio- and stereoselective C(sp2)−H alkenylation of N- pyridyl/ N-pyrimidylIndole and the N−H alkenylation of N-pyrimidylaniline derivatives with ynamides” under mild conditions using water as the solvent has been described (With includes recyclability of the catalytic system and details discussion of mechanistic as well as Kinetic studies). Finally, the preparation of catalyst [Re(CO)3(H2O)3]Br & characterization.
Chapter [C] was emphasis ruthenium (II)-catalyzed C−H/N−O bond functionalization of N- methoxybenzamides with alkynylsulfane in microwave-assisted is reported. These parts cover an exhaustive examination of mechanistic accompanied by kinetic studies to propose a logical mechanistic cycle.
Chapter [D] is metal and oxidant-free intramolecular C-N bond formation using oxazolineamide was described. This chapter also includes with introduction and results along with mechanism and characterization data.

並列關鍵字

Rhenium (I) & Ruthenium (II) catalyst ； C-H bond functionalization ； Water ； N-Pyridyl-/ N- pyrimidylindole ； 3-(phenylethynyl)oxazolidin-2-one ； N-Methoxybenzamides ； Alkynylsulfane ； Cesium Acetate ； Sodium Pivalate ； Metal & Oxidant Free ； p-Toluenesulfonic acid monohydrate ； Oxazolineamide ； Quinazolinones

參考文獻

1. a) S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda, N. Chatani, Nature 1993, 366, 529- 531; b) C. Jia, T. Kitamura, Y. Fujiwara, Acc. Chem. Res. 2001, 34, 633- 639; c) L. Ackermann, R. Vicente, A. R. Kapdi, Angew. Chem. Int. Ed. 2009, 48, 9792- 9826; d) T. W. Lyons, M. S. Sandford, Chem. Rev. 2010, 110, 1147- 1169; e) J. A. Palmes, A. Aponick, Synthesis 2012, 44, 3699–3721; f) G. Abbiati, F. Marinelli, E. Rossi, A. Arcadi, Isr. J. Chem. 2013, 53, 856–868; g) S. Mannathan, C. H. Cheng, J. Chin. Chem. Soc. 2014, 61, 59–66; h) G. Abbiati, A. Arcadi, F. Marinelli, E. Rossi, Synthesis 2014, 46, 687–721; i) J. R. Chen, X. Q. Hu, L. Q. Lu, W. J. Xiao, Chem. Rev. 2015, 115, 5301–5365.

2. For selected reviews on C–H bond activation, see a) X. Chen, K. M. Engle, D.-H. Wang, J.-Q. Yu, Angew. Chem. Int. Ed. 2009, 48, 5094–5115; Angew. Chem. 2009, 121, 5196; b) C.-J. Li, Acc. Chem. Res. , 42, 335–344; c) O. Daugulis, H.-Q. Do, D. Shabashov, Acc. Chem. Res. 2009, 42, 1074– 1086; d) E. Nakamura, N. Yoshikai, J. Org. Chem. 2010, 75, 6061–6067; e) L. Ackermann, Chem. Rev. 2011, 111, 1315–1345; f) C.-L. Sun, B.-J. Li, Z. J. Shi, Chem. Rev. 2011, 111, 1293–1314; g) S. H. Cho, J. Y. Kim, J. Kwak, S. Chang, Chem. Soc. Rev. 2011, 40, 5068–5083; h) L. McMurray, F. O'Hara, M. J. Gaunt, Chem. Soc. Rev. 2011, 40, 1885–1898; i) C. Zhang, C. Tang, N. Jiao, Chem. Soc. Rev. 2012, 41, 3464–3484; j) G. Song, F. Wang, X. Li, Chem. Soc. Rev. 2012, 41, 3651–3678; k) J. Wencel-Delord, F. Glorius, Nat. Chem. 2013, 5, 369–375; l) G. Rouquet, N. Chatani, Angew. Chem. Int. Ed. 2013, 52, 11726–11743; Angew. Chem. 2013, 125, 11942; m) C. Wang, Synlett 2013, 24, 1606–1613; n) K. Gao, N. Yoshikai, Acc. Chem. Res. 2014, 47, 1208–1218; o) R. He, Z.-T. Huang, Q.-Y. Zheng, C. Wang, Tetrahedron Lett. 2014, 55, 5705–5713; p) F. Jia, Z. Li, Org. Chem. Front. 2014, 1, 194– 214; q) Y. Yang, C. Wang, Sci. China Chem. 2015, 58, 1266–1279; r) Z. Chen, B. Wang, J. Zhang, W. Yu, Z. Liu, Y. Zhang, Org. Chem. Front. 2015, 2, 1107–1295. For selected reviews on C–C bond activation, see: s) M. Murakami, Y. Ito, Top. Organomet. Chem. 1999, 3, 97–129; t) C.-H. Jun, Chem. Soc. Rev. 2004, 33, 610–618; u) F. Chen, T. Wang, N. Jiao, Chem. Rev. 2014, 114, 8613–8661; v) M. Murakami, N. Ishida, J. Am. Chem. Soc. 2016, 138, 13759–13769; w) P. Chen, G. Dong, Chem. Eur. J. 2016, 22, 18290–18315; x) M. Tobisu, N. Chatani, Chem. Soc. Rev. 2008, 37, 300– 307; y) Y. Nakao, T. Hiyama, Pure Appl. Chem. 2008, 80, 1097–1107; z) A. Dermenci, J. W. Coe, G. Dong, Org. Chem. Front. 2014, 1, 567–581.

3. For recent reviews on rhenium catalysis, see a) Y. Kuninobu, K. Takai, Chem. Rev. 2011, 111, 1938–1953; b) G. Mao, B. Jia, C. Wang, Chin. J. Org. Chem. 2015, 35, 284–293. For selected examples on rhenium catalysis: c) H. Chen, J. F. Hartwig, Angew. Chem. Int. Ed. 1999, 38, 3391–3393; Angew. Chem. 1999, 111, 3597; d) R. Hua, X. Tian, J. Org. Chem. 2004, 69, 5782–5784; e) Y. Kuninobu, Y. Nishina, T. Matsuki, K. Takai, J. Am. Chem. Soc. 2008, 130, 14062–14063; f) Q. Liu, Y.-N. Li, H.-H. Zhang, B. Chen, C.- H. Tung, L.-Z. Wu, J. Org. Chem. 2011, 76, 1444–1447; g) D. Xia, Y. Wang, Z. Du, Q.-Y. Zheng, C. Wang, Org. Lett. 2012, 14, 588–591; h) Y. Fukumoto, M. Daijo, N. Chatani, J. Am. Chem. Soc. 2012, 134, 8762–8765; i) H. Peng, A. Lin, Y. Zhang, H. Jiang, J. Zhou, Y. Cheng, C. Zhu, H. Hu, ACS Catal. 2012, 2, 163–167; j) Y. Wang, L. Zhang, Y. Yang, P. Zhang, Z. Du, C. Wang, J. Am. Chem. Soc. 2013, 135, 18048–18051; k) Q. Tang, D. Xia, X. Jin, Q. Zhang, X.-Q. Sun, C. Wang, J. Am. Chem. Soc. 2013, 135, 4628–4631; l) H. Jin, J. Xie, C. Pan, Z. Zhu, Y. Cheng, C. Zhu, ACS Catal. 2013, 3, 2195– 2198; m) Y. Sun, H. Chen, J. Chem. Theory Comput. 2014, 10, 579–588; n) X. Geng, C. Wang, Org. Lett. 2015, 17, 2434–2437; o) H. Gu, C. Wang, Org. Biomol. Chem. 2015, 13, 5880–5884; p) X. Geng, C. Wang, Org. Biomol. Chem. 2015, 13, 7619–7623; q) H. Jin, Z. Zhu, N. Jin, J. Xie, Y. Cheng, C. Zhu, Org. Chem. Front. 2015, 2, 378–382; r) X. Jin, X. Yang, Y. Yang, C. Wang, Org. Chem. Front. 2016, 3, 268–272.

4. a) B. M. Trost, M. J. Krische, Synlett, 1998, 1–16; b) T.-Y. Luh, M.-K. Leung, K.-T. Wong, Chem. Rev. 2000, 100, 3187–3204; c) C. H. Jun, Chem. Soc. Rev. 2004, 33, 610–618; d) W. Shi, C. Liu, A. Lei, Chem. Soc. Rev. 2011, 40, 2761–2776; e) K. Huang, C.-L. Sun, Z.-J. Shi, Chem. Soc. Rev. 2011, 40, 2435–2452; f) S. G. Modha, V. P. Mehta, E. V. Van der Eycken, Chem. Soc. Rev. 2013, 42, 5042–5055; g) G. Brahmachari, RSC Adv. 2016, 6, 64676–64725.

5. a) W. M. Czaplik, M. Mayer, J. Cvengros, A. J. von Wangelin, ChemSusChem 2009, 2, 396–417; b) C. C. C. Johansson Seechurn, M. O. Kitching, T. J. Colacot, V. Snieckus, Angew. Chem. Int. Ed. 2012, 51, 5062–5085; Angew. Chem. 2012, 124, 5150–5174; c) T. L. Mako, J. A. Byers, Inorg. Chem. Front. 2016, 3, 766–790; d) N. Hazari, P. R. Melvin, M. M. Beromi, Nat. Rev. Chem. 2017, 1, 0025; e) K. Zhao, L. Shen, Z.-L. Shen, T.-P. Loh, Chem. Soc. Rev. 2017, 46, 586–602.