Rhodium-Catalyzed Enantioselective Spiroannulation of 2-Alkenylphenols with Alkynes

doi:10.6023/cjoc202303021

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (8): 2926-2933.DOI: 10.6023/cjoc202303021 Previous Articles Next Articles

铑催化2-烯基苯酚与炔烃的对映体选择性螺环化反应

张素珍^a^,^b, 张文文^b, 杨慧^b, 顾庆^b^,^*(), 游书力^b^,^*()

a 上海理工大学材料与化学学院上海 200093
b 中国科学院上海有机化学研究所金属有机化学国家重点实验室上海 200032

收稿日期:2023-03-15 修回日期:2023-03-28 发布日期:2023-04-07
基金资助:
国家自然科学基金(21821002); 国家自然科学基金(92256302); 国家自然科学基金(22071260)

Rhodium-Catalyzed Enantioselective Spiroannulation of 2-Alkenylphenols with Alkynes

Suzhen Zhang^a^,^b, Wenwen Zhang^b, Hui Yang^b, Qing Gu^b(), Shuli You^b()

a School of Material and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2023-03-15 Revised:2023-03-28 Published:2023-04-07
Contact: *E-mail: qinggu@sioc.ac.cn, slyou@sioc.ac.cn
Supported by:
The National Natural Science Foundation of China(21821002); The National Natural Science Foundation of China(92256302); The National Natural Science Foundation of China(22071260)

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Abstract

Rh-catalyzed enantioselective spiroannulation of 2-alkenylphenols with alkynes was developed. In the presence of 5 mol% BINOL-derived (BINOL: 1,1'-bi-2,2'-naphthol) cyclopentadiene-Rh complex [(R)-CpRh1] and 2 equiv. of Cu(O- Ac)₂, the C—H activation/annulation reaction proceeded smoothly to afford a wide range of enantioenriched spirocyclohexenones in up to 84% yield and 81% ee. This reaction features mild reaction conditions and good functional group tolerance.

Key words: 2‑alkenylphenol, alkyne, cyclopentadiene-Rh complex, spiroannulation, spirocyclohexenone

Cite this article

Suzhen Zhang, Wenwen Zhang, Hui Yang, Qing Gu, Shuli You. Rhodium-Catalyzed Enantioselective Spiroannulation of 2-Alkenylphenols with Alkynes[J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2926-2933.

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References 9

[1]	For reviews on transition-metal-catalyzed C—H activation/annul- ation reactions, see: (a) Satoh, T.; Miura, M. Chem.-Eur. J. 2010, 16, 11212. doi: 10.1002/chem.v16:37
	(b) Ackermann, L. Acc. Chem. Res. 2014, 47, 281. doi: 10.1021/ar3002798
	(c) Yang, Y.; Li, K.; Cheng, Y.; Wan, D.; Li, M.; You, J. Chem. Commun. 2016, 52, 2872. doi: 10.1039/C5CC09180B
	(d) Duarah, G.; Kaishap, P. P.; Begum, T.; Gogoi, S. Adv. Synth. Catal. 2019, 361, 654. doi: 10.1002/adsc.201800755
	(d) Kuang, G.; Liu, G.; Zhang, X.; Lu, N.; Peng, Y.; Xiao, Q.; Zhou, Y. Synthesis 2020, 52, 993. doi: 10.1055/s-0039-1690816
	(e) Saha, A.; Shankar, M.; Sau, S.; Sahoo, A. K. Chem. Commun. 2022, 58, 4561. doi: 10.1039/D2CC00172A
	Selected reviews on transition-metal-catalyzed C—H functionalizations, see: (f) Ji, Y.; Zhang, M.; Xing, M.; Cui, H.; Zhao, Q.; Zhang, C. Chin. J. Chem. 2021, 39, 391. doi: 10.1002/cjoc.v39.2
	(g) Liu, X.; Kuang, C.; Su, C. Acta Chim. Sinica 2022, 80, 1135. (in Chinese) doi: 10.6023/A22040147
	( 刘霞, 匡春香, 苏长会, 化学学报, 2022, 80, 1135.) doi: 10.6023/A22040147
	(h) Gu, H.; Jin, X.; Li, J.; Li, H.; Liu, J. Chin. J. Org. Chem. 2022, 42, 2682. (in Chinese) doi: 10.6023/cjoc202204056
	( 顾海春, 靳新新, 李嘉琪, 李贺, 刘景林, 有机化学, 2022, 42, 2682.) doi: 10.6023/cjoc202204056
[2]	(a) Reddy Chidipudi, S.; Khan, I.; Lam, H. W. Angew. Chem., Int. Ed. 2012, 51, 12115. doi: 10.1002/anie.201207170
	(b) Dooley, J. D.; Reddy Chidipudi, S.; Lam, H. W. J. Am. Chem. Soc. 2013, 135, 10829. doi: 10.1021/ja404867k
	(c) Reddy Chidipudi, S.; Burns, D. J.; Khan, I.; Lam, H. W. Angew. Chem., Int. Ed. 2015, 54, 13975. doi: 10.1002/anie.v54.47
[3]	(a) Nan, J.; Zuo, Z.; Luo, L.; Bai, L.; Zheng, H.; Yuan, Y.; Liu, J.; Luan, X.; Wang, Y. J. Am. Chem. Soc. 2013, 135, 17306. doi: 10.1021/ja410060e
	(b) Han, L.; Wang, H.; Luan, X. Org. Chem. Front. 2018, 5, 2453. doi: 10.1039/C8QO00614H
	(c) Hao, J.; Ge, Y.; Yang, L.; Wang, J.; Luan, X. Tetrahedron Lett. 2021, 71, 153050. doi: 10.1016/j.tetlet.2021.153050
	(d) Li, K.; Bai, L.; Luan, X. Chin. J. Org. Chem. 2019, 39, 2211. (in Chinese) doi: 10.6023/cjoc201903065
	( 李锟雨, 白璐, 栾新军, 有机化学, 2019, 39, 2211.) doi: 10.6023/cjoc201903065
	(e) Li, H.; Cui, X. Chin. J. Org. Chem. 2020, 40, 543. (in Chinese) doi: 10.6023/cjoc202000007
	( 李欢, 崔秀灵, 有机化学, 2020, 40, 543.) doi: 10.6023/cjoc202000007
[4]	(a) Zheng, J.; Wang, S.-B.; Zheng, C.; You, S.-L. J. Am. Chem. Soc. 2015, 137, 4880. doi: 10.1021/jacs.5b01707 pmid: 25853771
	(b) Zheng, C.; Zheng, J.; You, S.-L. ACS Catal. 2016, 6, 262. doi: 10.1021/acscatal.5b01891 pmid: 25853771
[5]	Other examples of enantioselective C—H spiroannulation reactions with alkynes, see: (a) Zhang, M.; Huang, G. Chem. Eur. J. 2016, 22, 9356. doi: 10.1002/chem.201600884
	(b) Zheng, J.; Wang, S.-B.; Zheng, C.; You, S.-L. Angew. Chem., Int. Ed. 2017, 56, 4540. doi: 10.1002/anie.201700021
	(c) Duarah, G.; Kaishap, P. P.; Sarma, B.; Gogoi, S. Chem. Eur. J. 2018, 24, 10196. doi: 10.1002/chem.v24.40
	(d) Li, H.; Gontla, R.; Flegel, J.; Merten, C.; Ziegler, S.; Antonchick, A. P.; Waldmann, H. Angew. Chem., Int. Ed. 2019, 58, 307. doi: 10.1002/anie.201811041
	(e) Huang, Y.-Q.; Wu, Z.-J.; Zhu, L.; Gu, Q.; Lu, X.; You, S.-L.; Mei, T.-S. CCS Chem. 2022, 4, 3181. doi: 10.31635/ccschem.021.202101376
	(f) Wang, Y.; Huang, X.; Wang, Q.; Tang, Y.; Xu, S.; Li, Y. Org. Lett. 2021, 23, 757. doi: 10.1021/acs.orglett.0c03982
	(g) Wei, W.; Scheremetjew, A.; Ackermann, L. Chem. Sci. 2022, 13, 2783. doi: 10.1039/D1SC07124F
[6]	For C—H spiroannulation reactions of phenols with alkynes in a racemic manner, see: (a) Seoane, A.; Casanova, N.; Quinones, N.; Mascareñas, J. L.; Gulias, M. J. Am. Chem. Soc. 2014, 136, 7607. doi: 10.1021/ja5034952
	(b) Kujawa, S.; Best, D.; Burns, D. J.; Lam, H. W. Chem. Eur. J. 2014, 20, 8599. doi: 10.1002/chem.201403454
	(c) Zuo, Z.; Yang, X.; Liu, J.; Nan, J.; Bai, L.; Wang, Y.; Luan, X. J. Org. Chem. 2015, 80, 3349. doi: 10.1021/acs.joc.5b00316
	(d) Lin, P.-P.; Han, X.-L.; Ye, G.-H.; Li, J.-L.; Li, Q.; Wang, H. J. Org. Chem. 2019, 84, 12966. doi: 10.1021/acs.joc.9b01750
	(e) Liu, A.; Han, K.; Wu, X.-X.; Chen, S.; Wang, J. Chin. J. Chem. 2020, 38, 1257. doi: 10.1002/cjoc.v38.11
	(f) Liu, T.; Han, L.; Zhang, J.; Lu, G. J. Org. Chem. 2021, 86, 10484.
[7]	(a) Pettus, T. R. R.; Inoue, M.; Chen, X.-T.; Danishefsky, S. J. J. Am. Chem. Soc. 2000, 122, 6160. doi: 10.1021/ja000521m pmid: 31008606
	(b) Zhan, Z.-J.; Li, C.-P.; Shan, W.-G. J. Chem. Res. 2007, 1, 38. pmid: 31008606
	(c) Saito, Y.; Takashima, Y.; Kamada, A.; Suzuki, Y.; Suenaga, M.; Okamoto, Y.; Matsunaga, Y.; Hanai, R.; Kawahara, T.; Gong, X.; Tori, M.; Kuroda, C. Tetrahedron 2012, 68, 10011. doi: 10.1016/j.tet.2012.09.042 pmid: 31008606
	(d) Sandargo, B.; Michehl, M.; Praditya, D.; Steinmann, E.; Stadler, M.; Surup, F. Org. Lett. 2019, 21, 3286. doi: 10.1021/acs.orglett.9b01017 pmid: 31008606
[8]	For selected reviews on Rh-catalyzed C—H functionalizations, see: (a) Ye, B.; Cramer, N. Acc. Chem. Res. 2015, 48, 1308. doi: 10.1021/acs.accounts.5b00092
	(b) Yoshino, T.; Satake, S.; Matsunaga, S. Chem. Eur. J. 2020, 26, 7346. doi: 10.1002/chem.v26.33
	(c) Shaaban, S.; Davies, C.; Waldmann, H. Eur. J. Org. Chem. 2020, 6512.
	(d) Mas-Rosello, J.; Herraiz, A. G.; Audic, B.; Laverny, A.; Cramer, N. Angew. Chem., Int. Ed. 2021, 60, 13198. doi: 10.1002/anie.v60.24
	(e) Davies, C.; Shaaban, S.; Waldmann, H. Trends Chem. 2022, 4, 318. doi: 10.1016/j.trechm.2022.01.005
[9]	(a) Ye, B.; Cramer, N. Science 2012, 338, 504. doi: 10.1126/science.1226938 pmid: 27070297
	(b) Ye, B.; Cramer, N. J. Am. Chem. Soc. 2013, 135, 636. doi: 10.1021/ja311956k pmid: 27070297
	(c) Zheng, J.; Cui, W.-J.; Zheng, C.; You, S.-L. J. Am. Chem. Soc. 2016, 138, 5242. doi: 10.1021/jacs.6b02302 pmid: 27070297

Entry	[Rh]	Solvent	Yield^b/%	ee^c/%
1	(R)-CpRh1	CH₃CN	48	74
2	(R)-CpRh2	CH₃CN	60	40
3	(R)-CpRh3	CH₃CN	50	60
4	(R)-CpRh4	CH₃CN	39	56
5	(R)-CpRh5	CH₃CN	8	39
6	(S)-SCpRh1	CH₃CN	18	54
7	(S)-SCpRh2	CH₃CN	60	38
8^d	(R)-CpRh1	CH₃CN	52	76
9^d	(R)-CpRh1	^tAmylOH	60	75
10^d	(R)-CpRh1	1,4-Dioxane	14	83
11^d	(R)-CpRh1	THF	21	80
12^d	(R)-CpRh1	DMF	31	70
13^d	(R)-CpRh1	1,4-Dioxane/^tAmylOH	42	77
14^d	(R)-CpRh1	THF/^tAmylOH	52	76
15^d	(R)-CpRh1	DMF/^tAmylOH	81 (77^e)	81

Entry	[Rh]	Solvent	Yield^b/%	ee^c/%
1	(R)-CpRh1	CH₃CN	48	74
2	(R)-CpRh2	CH₃CN	60	40
3	(R)-CpRh3	CH₃CN	50	60
4	(R)-CpRh4	CH₃CN	39	56
5	(R)-CpRh5	CH₃CN	8	39
6	(S)-SCpRh1	CH₃CN	18	54
7	(S)-SCpRh2	CH₃CN	60	38
8^d	(R)-CpRh1	CH₃CN	52	76
9^d	(R)-CpRh1	^tAmylOH	60	75
10^d	(R)-CpRh1	1,4-Dioxane	14	83
11^d	(R)-CpRh1	THF	21	80
12^d	(R)-CpRh1	DMF	31	70
13^d	(R)-CpRh1	1,4-Dioxane/^tAmylOH	42	77
14^d	(R)-CpRh1	THF/^tAmylOH	52	76
15^d	(R)-CpRh1	DMF/^tAmylOH	81 (77^e)	81

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铑催化2-烯基苯酚与炔烃的对映体选择性螺环化反应

Rhodium-Catalyzed Enantioselective Spiroannulation of 2-Alkenylphenols with Alkynes

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