ent-Kaurene全碳骨架中AB环系的不对称合成
收稿日期: 2021-08-17
修回日期: 2021-09-16
网络出版日期: 2022-02-24
基金资助
安徽省高校自然科学一般项目(KJ2020B19); 滁州学院启动基金(2018qd06)
Asymmetric Synthesis of AB Rings in ent-Kaurene Carbon Framework
Received date: 2021-08-17
Revised date: 2021-09-16
Online published: 2022-02-24
Supported by
Anhui University Natural Science Foundation-Funded Project(KJ2020B19); Chuzhou University Initial Funding(2018qd06)
本课题组前期利用多样性导向合成策略完成ent-kaurene天然产物Xerophilusin I、Neolaxiflorin L、Eriocalyxin B、15-epi-Enmelol全合成工作, 为完成该类天然产物的不对称合成, 对Horner-Wadsworth-Emmons反应进行了优化, 改善了反应的区域选择性, 在酸性条件下后处理, 将Z/E混合物转化为单一Z构型. 基于温和的酸性条件实现了单一构型的转化, 提出了氢键辅助的Michael加成/retro-Michael消除的机理猜想. 发展了Cu(OTf)2催化的不对称Diels-Alder反应: 以烯醇硅醚的双烯体3、β-酮酸酯1为亲双烯体, 在噁唑啉为手性配体的条件下, 以65%的收率和>19∶1 dr值完成AB环的构建.
马文静 , 朱礼志 , 章梦珣 , 李志成 . ent-Kaurene全碳骨架中AB环系的不对称合成[J]. 有机化学, 2022 , 42(2) : 580 -589 . DOI: 10.6023/cjoc202108029
The total synthesis of ent-kaurene natural products of Xerophilusin I, Neolaxiflorin L, Eriocalyxin B, 15-epi- Enmelol completed by diversity-oriented synthesis strategy. In this paper, the regioselectivity of Horner-Wadsworth-Emmons reaction was optimized, and a single Z configuration was transformed from Z/E mixture under acidic condition. Based on the conversion of a single configuration under mild acidic conditions, a mechanism for hydrogen bond-assisted Michael addition/retro-Michael elimination is proposed. The asymmetric Diels-Alder reaction with silylenol ether dienyl 3 and β-ketoate 1 as dienophile was developed. Using Cu(OTf)2 as Lewis acid and oxazoline as chiral ligand, AB-ring-skeleton was constructed with 65% yield and >19∶1 dr value.
| [1] | (a) García, P. A.; De Oliveira, A. B.; Batista, R. Molecules 2007, 12, 455. |
| [1] | (b) Sun, H. D.; Huang, S. X.; Han, Q. B. Nat. Prod. Rep. 2006, 23, 673. |
| [1] | (c) Liu, M.; Wang, W. G.; Sun, H. D.; Pu, J. X. Nat. Prod. Rep. 2017, 34, 1090. |
| [2] | Quitt, P.; Mosettig, E.; Cambie, R. C.; Rutledge, P. S.; Briggs, L. H. J. Am. Chem. Soc. 1961, 83, 3720. |
| [3] | For the structure-activity relationship of ent-kaurane diterpenoids and derivatives, see: (a) Li, X.; Pu, J. X.; Weng, Z. Y.; Zhao, Y.; Zhao, W. L.; Sun, H. D. Chem. Biodiversity. 2010, 7, 2888. |
| [3] | (b) Ding, C. Y.; Zhang, Y. S.; Chen, H. J.; Yang, Z. D.; Wild, C.; Chu, L. L.; Liu, H. L.; Shen, Q.; Zhou, J. J. Med. Chem. 2013, 56, 5048. |
| [3] | (c) Ding, C. Y.; Zhang, Y. S.; Chen, H. J.; Yang, Z. D.; Wild, C.; Ye, N.; Ester, C. D.; Xiong, A. L.; White, M. A.; Shen, Q.; Zhou, J. J. Med. Chem. 2013, 56, 8814. |
| [3] | (d) Yeoman, J. T.; Mak, V. W.; Reisman, S. E. J. Am. Chem. Soc. 2013, 135, 11764. |
| [3] | (e) Lazarski, K. E.; Moritz, B. J.; Thomson, R. J. Angew. Chem., Int. Ed. 2014, 53, 10588. |
| [3] | (f) Pan, Z. Q.; Zheng, C. Y.; Wang, H. Y.; Chen, Y. H.; Li, Y.; Cheng, B.; Zhai, H. B. Org. Lett. 2014, 16, 216. |
| [3] | (g) Moritz, B. J.; Mack, D. J.; Tong, L. C.; Thomson, R. J. Angew. Chem., Int. Ed. 2014, 53, 2988. |
| [3] | (h) Wang, W. G.; Yang, J.; Wu, H. Y.; Kong, L. M.; Su, J.; Li, X. N.; Du, X.; Zhan, R.; Zhou, M.; Li, Y.; Pu, J. X.; Sun, H. D. Tetrahedron 2015, 71, 9161. |
| [3] | (i) Ding, Y.; Ding, C.; Ye, N.; Liu, Z.; Wold, E. A.; Chen, H.; Wild, C.; Shen, Q.; Zhou, J. Eur. J. Med. Chem. 2016, 122, 102. |
| [3] | (j) Li, D.; Han, T.; Liao, J.; Hu, X.; Xu, S.; Tian, K.; Gu, X.; Cheng, K.; Li, Z.; Hua, H.; Xu, J. Int. J. Mol. Sci. 2016, 17, 1395. |
| [3] | (k) Wu, J.; Ding, Y.; Chen, C. H.; Zhou, Z. M.; Ding, C. Y.; Chen, H. Y.; Zhou, J.; Chen, C. S. Cancer Lett. 2016, 380, 393. |
| [3] | (l) Chen, W.; Zhou, J.; Wu, K.; Huang, J.; Ding, Y.; Yun, E. J.; Wang, B.; Ding, C.; Hernandez, E.; Santoyo, J.; Chen, H.; Lin, H.; Sagalowsky, A.; He, D.; Zhou, J.; Hsieh, J. T. Oncotarget 2016, 7, 56842. |
| [3] | (m) Liu, Q. Q.; Wang, H. L.; Chen, K.; Wang, S. B.; Xu, Y.; Ye, Q.; Sun, Y. W. J. Dig. Dis. 2016, 17, 104. |
| [3] | (n) Xu, S.; Yao, H.; Luo, S.; Zhang, Y.; Yang, D.; Li, D.; Wang, G.; Hu, M.; Qiu, Y.; Wu, X. J. Med. Chem. 2017, 60, 1449. |
| [3] | (o) Xu, S.; Yao, H.; Hu, M.; Li, D.; Zhu, Z.; Xie, W.; Yao, H.; Wu, L.; Chen, Z.; Xu, J. J. Nat. Prod. 2017, 80, 2391. |
| [3] | (p) Xu, J.; Wold, E. A.; Ding, Y.; Shen, Q.; Zhou, J. Molecules 2018, 23, 474. |
| [3] | (q) Wang, M.; He, L.; Xu, F.; Gao, X.; Li, J.; Xu, S.; Zhang, D.; Wu, X.; Xu, J.; Hua, H.; Li, D. Eur. J. Med. Chem. 2018, 156, 885. |
| [3] | (r) Li, H.;, Jiao, R.; Mu, J.; Xu, L.; Wang, X.; Li, Z.; Xu, J.; Hua, H.; Li, D. Molecules 2018, 23, 2914. |
| [3] | (s) Luo, D.; Yi, Y.; Peng, K.; Liu, T.; Yang, J.; Liu, S.; Zhao, W.; Qu, X.; Yu, W.; Gu, Y.; Wan, S. Eur. J. Med. Chem. 2019, 178, 365. |
| [3] | (t) Zhang, M.; Lee, M. M. L.; Ye, W.; Wong, W. Y.; Chan, B. D.; Chen, S.; Zhu, L.; Tai, W. C. S.; Lee, C. S. J. Org. Chem. 2019, 84, 7007. |
| [3] | (u) Hu, X.; Wang, Y.; Gao, X.; Xu, S.; Zang, L.; Xiao, Y.; Li, Z.; Hua, H.; Xu, J.; Li, D. Mini-Rev. Med. Chem. 2020, 20, 483. |
| [4] | For reviews of ent-kauranoid total synthesis, see: (a) Lazarski, K. E.; Moritz, B. J.; Thomson, R. J. Angew. Chem., nt. Ed. 2014, 53, 10588. |
| [4] | (b) Zhu, L.; Huang, S. H.; Yu, J.; Hong, R. Tetrahedron Lett. 2015, 56, 23. |
| [4] | (c) Du, M.; Lei, X. Chin. J. Org. Chem. 2015, 35, 2447. (in Chinese) |
| [4] | ( 杜明军, 雷晓光, 有机化学, 2015, 35, 2447.) |
| [4] | (d) Riehl, P. S.; DePorre, Y. C.; Armaly, A. M.; Groso, E. J.; Schindler, C. S. Tetrahedron 2015, 71, 6629. |
| [4] | (e) Zhao, X.; Cacherat, B.; Hu, Q.; Ma, D. Nat. Prod. Rep. 2022, 39, 119. |
| [5] | For selected total syntheses of ent-kaurane diterpenoids with an intact ent-kaurane skeleton, see: (a) Bell, R. A.; Ireland, R. E.; Partyka, R. A. J. Org. Chem. 1962, 27, 3741. |
| [5] | (b) Bell, R. A.; Ireland, R. E.; Partyka, R. A. J. Org. Chem. 1966, 31, 2530. |
| [5] | (c) Mori, K.; Nakahara, Y.; Matsui, M. Tetrahedron 1972, 28, 3217. |
| [5] | (d) Ziegler, F. E.; Kloek, J. A. Tetrahedron 1977, 33, 373. |
| [5] | (e) Corey, E. J.; Wess, G.; Xiang, Y. B.; Singh, A. K. J. Am. Chem. Soc. 1987, 109, 4717. |
| [5] | (f) Singh, A. K.; Bakshi, R. K.; Corey, E. J. J. Am. Chem. Soc. 1987, 109, 6187. |
| [5] | (g) Corey, E. J.; Liu, K. J. Am. Chem. Soc. 1997, 119, 9929. |
| [5] | (h) Abad, A.; Agullo, C.; Cunat, A. C.; de Alfonso Marzal, I.; Navarro, I.; Gris, A. Tetrahedron 2006, 62, 3266. |
| [5] | (i) Cherney, E. C.; Green, J. C.; Baran, P. S. Angew. Chem., Int. Ed. 2013, 52, 9019. |
| [5] | (j) Yeoman, J. T. S.; Mak, V. W.; Reisman, S. E. J. Am. Chem. Soc. 2013, 135, 11764. |
| [5] | (k) Zhu, L.; Luo, J.; Hong, R. Org. Lett. 2014, 16, 2162. |
| [5] | (l) Zhao, X.; Li, W.; Wang, J.; Ma, D. J. Am. Chem. Soc. 2017, 139, 2932. |
| [5] | (m) He, C.; Hu, J.; Wu, Y.; Ding, H. J. Am. Chem. Soc. 2017, 139, 6098. |
| [5] | (n) Su, F.; Lu, Y.; Kong, L.; Liu, J.; Luo, T. Angew. Chem., Int. Ed. 2018, 57, 760. |
| [5] | (o) Zhu, L.; Ma, W.; Zhang, M.; Lee, M. M. L.; Wong, W. Y.; Chan, B. D.; Yang, Q.; Wong, W. T.; Tai, W. C. S.; Lee, C. S. Nat. Commun. 2018, 9, 1283. |
| [5] | (p) Hong, B.; Liu, W.; Wang, J.; Wu, J.; Kadonaga, Y.; Cai, P.; Lou, H.; Yu, Z.; Li, H.; Lei, X. Chem 2019, 5, 1671. |
| [5] | (q) Wang, J.; Ma, D. Angew. Chem., Int. Ed. 2019, 58, 15731. |
| [5] | (r) Kong, L.; Su, F.; Yu, H.; Jiang, Z.; Lu, Y.; Luo, T. J. Am. Chem. Soc. 2019, 141, 20048. |
| [5] | (s) Guo, J.; Li, B.; Ma, W.; Mallesham, P.; Jia, Y. Angew. Chem., Int. Ed. 2020, 132, 15307. |
| [5] | (t) Xu, Z.; Zong, Y.; Qiao, Y.; Zhang, J.; Liu, X.; Zhu, M.; Xu, Y.; Zheng, H.; Fang, L.; Wang, X.; Lou, H. Angew. Chem.,Int. Ed. 2020, 132, 20091. |
| [5] | (u) Liu, W.; Yue, Z.; Wang, Z.; Li, H.; Lei, X. Org. Lett. 2020, 22, 7991. |
| [6] | For selected syntheses of ent-kaurane diterpenoids with a rearranged or cleaved ent-kaurane skeleton, see: (a) Fujita, E.; Shibuya, M.; Nakamura, S.; Okada, Y.; Fujita, T. J. Chem. Soc., Perkin Trans. 1974, 22, 165. (a),.;,.;,.;,.;,. |
| [6] | (b) Paquette, L. A.; Backhaus, D.; Braun, R. J. Am. Chem. Soc. 1996, 118, 11990. |
| [6] | (c) Gong, J.; Lin, G.; Sun, W.; Li, C. C.; Yang, Z. J. Am. Chem. Soc. 2010, 132, 16745. |
| [6] | (d) Cha, J. Y.; Yeoman, J. T. S.; Reisman, S. E. J. Am. Chem. Soc. 2011, 133, 14964. |
| [6] | (e) Peng, F.; Danishefsky, S. J. J. Am. Chem. Soc. 2012, 134, 18860. |
| [6] | (f) Lu, P.; Gu, Z.; Zakarian, A. J. Am. Chem. Soc. 2013, 135, 14552. |
| [6] | (g) Breitler, S.; Carreira, E. M. Angew. Chem.,Int. Ed. 2013, 52, 11168. |
| [6] | (h) Lu, P.; Mailyan, A.; Gu, Z.; Guptill, D. M.; Wang, H.; Davies, H. M. L.; Zakarian, A. J. Am. Chem. Soc. 2014, 136, 17738. |
| [6] | (i) Zheng, C.; Dubovyk, I.; Lazarski, K. E.; Thomson, R. J. J. Am. Chem. Soc. 2014, 136, 17750. |
| [6] | (j) Moritz, B. J.; Mack, D. J.; Tong, L.; Thomson, R. J. Angew. Chem., nt. Ed. 2014, 53, 2988. |
| [6] | (k) Pan, Z.; Zheng, C.; Wang, H.; Chen, Y.; Li, Y.; Cheng, B.; Zhai, H. Org. Lett. 2014, 16, 216. |
| [6] | (l) Song, L.; Zhu, G.; Liu, Y.; Liu, B.; Qin, S. J. Am. Chem. Soc. 2015, 137, 13706. |
| [6] | (m) Cheng, H.; Zeng, F. H.; Yang, X.; Meng, Y. J.; Xu, L.; Wang, F. P. Angew. Chem., Int. Ed. 2016, 55, 392. |
| [6] | (n) Cernijenko, A.; Risgaard, R.; Baran, P. S. J. Am. Chem. Soc. 2016, 138, 9425. |
| [6] | (o) Liu, W.; Li, H.; Cai, P. J.; Wang, Z.; Yu, Z. X.; Lei, X. Angew. Chem., Int. Ed. 2016, 55, 3112. |
| [6] | (p) Lv, Z.; Chen, B.; Zhang, C.; Liang, G. Chem.-Eur. J. 2018, 24, 9773. |
| [6] | (q) Wu, J.; Kadonaga, Y.; Hong, B.; Wang, J.; Lei, X. Angew. Chem., nt. Ed. 2019, 58, 10879. |
| [6] | (r) Zhang, J.; Li, Z.; Zhuo, J.; Cui, Y.; Han, T.; Li, C. J. Am. Chem. Soc. 2019, 141, 8372. |
| [6] | (s) Wein, L. A.; Wurst, K.; Angyal, P.; Weisheit, L.; Magauer, T. J. Am. Chem. Soc. 2019, 141, 19589. |
| [6] | (t) Chen, R.; Zhang, F.; Hua, Y.; Shi, D.; Lei, X.; Xiao, H.; Wang, Y.; Ding, S.; Shen, Y.; Zhang, Y. CCS Chem. 2021, 3, 1138. |
| [6] | (u) Wang, B.; Liu, Z.; Tong, Z.; Gao, B.; Ding, H. Angew. Chem., Int. Ed. 2021, 133, 15018. |
| [7] | Fabio, E. S. S.; Hamish, S. S.; Rina, C.; Russell, R. J. Org. Chem. 2002, 67, 6568. |
| [8] | Bernd, S.; Oliver, K.; Monib, H. P. J. Org. Chem. 2012, 77, 10897. |
| [9] | Clark, R. D., & Heathcock, C. H. Kozar, L. G. Synthesis (Stuttg.) 1975, 635. |
| [10] | Liao, S. H.; Sun, X. L.; Tang, Y. Acc. Chem. Res. 2014, 47, 2260. |
/
| 〈 |
|
〉 |
