Rhodium-Catalyzed C–C Bond Olefination of Ring-Fused Benzocyclobutenols and Application in the Construction of Polycyclic Compounds

Wenbin Mao; Chen Zhu

doi:10.1055/s-0036-1590830

Synlett, Table of Contents

Synlett 2018; 29(06): 731-735
DOI: 10.1055/s-0036-1590830

cluster

Rhodium-Catalyzed C–C Bond Olefination of Ring-Fused Benzocyclobutenols and Application in the Construction of Polycyclic Compounds

Authors

Wenbin Mao

^aKey Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu 215123, P. R. of China
Chen Zhu *

^aKey Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu 215123, P. R. of China

^bKey Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China Email: chzhu@suda.edu.cn

Abstract

All articles of this category

Published as part of the Cluster C–C Activation

Abstract

A novel rhodium-catalyzed C–C bond olefination of ring-fused benzocyclobutenols with ethyl acrylate is described. A variety of versatile olefinated products were efficiently generated at room temperature and then readily converted into many useful polycyclic compounds by one-step processes. The reaction provides a practical C–C bond olefination method with high atom efficiency.

Key words

rhodium catalysis - olefination - polycyclic compounds - atom efficiency - benzocyclobutenols

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References

References and Notes
1 Rybtchinski BB. Milstein D. Angew. Chem. Int. Ed. 1999; 38: 870

For selected reviews on C–C activation, see:

2a Jun C.-H. Chem. Soc. Rev. 2004; 33: 610
2b Park YJ. Park J.-W. Jun C.-H. Acc. Chem. Res. 2008; 41: 222
2c Aїssa C. Synthesis 2011; 3389
2d Murakami M. Matsuda T. Chem. Commun. 2011; 47: 1100
2e Ruhland K. Eur. J. Org. Chem. 2012; 2683
2f Chen F. Wang T. Jiao N. Chem. Rev. 2014; 114: 8613
2g Dermenci A. Coe JW. Dong G. Org. Chem. Front. 2014; 1: 567

3a Satoh T. Jones WD. Organometallics 2001; 20: 2916
3b Nishimura T. Araki H. Maeda Y. Uemura S. Org. Lett. 2003; 5: 2997
3c Kita Y. Tobisu M. Chatani N. Org. Lett. 2010; 12: 1864
3d Sugihara T. Satoh T. Miura M. Nomura M. Angew. Chem. Int. Ed. 2003; 42: 4672
3e Li H. Li Y. Zhang X.-S. Chen K. Wang X. Shi Z.-J. J. Am. Chem. Soc. 2011; 133: 15244

For selected reviews, see:

4a Sadana AK. Saini RK. Billups WE. Chem. Rev. 2003; 103: 1539
4b Seiser T. Cramer N. Org. Biomol. Chem. 2009; 7: 2835
4c Seiser T. Saget T. Tran DN. Cramer N. Angew. Chem. Int. Ed. 2011; 50: 7740
4d Flores-Gaspar A. Martin R. Synthesis 2013; 45: 563
4e Souillart L. Parker E. Cramer N. Top. Curr. Chem. 2014; 346: 163
4f Xu T. Dermenci A. Dong G. Top. Curr. Chem. 2014; 346: 233
4g Marek I. Masarwa A. Delaye P. Leibeling M. Angew. Chem. Int. Ed. 2015; 54: 414
4h Souillart L. Cramer N. Chem. Rev. 2015; 115: 9410
4i Fan X. Zhao H. Zhu C. Huaxue Xuebao 2015; 73: 979
4j Ren R. Zhu C. Synlett 2016; 27: 1139
4k Yan H. Zhu C. Sci. China: Chem. 2017; 60: 214

For transition-metal-catalyzed examples, see:

5a Nishimura T. Ohe K. Uemura S. J. Am. Chem. Soc. 1999; 121: 2645
5b Nishimura TT. Uemura S. J. Am. Chem. Soc. 1999; 121: 11010
5c Nishimura T. Matsumura S. Maeda Y. Uemura S. Chem. Commun. 2002; 50
5d Matsumura S. Maeda Y. Nishimura T. Uemura S. J. Am. Chem. Soc. 2003; 125: 8862
5e Seiser T. Cramer N. J. Am. Chem. Soc. 2010; 132: 5340
5f Chtchemelinine A. Rosa D. Orellana A. J. Org. Chem. 2011; 76: 9157
5g Rosa D. Chtchemelinine A. Orellana A. Synthesis 2012; 44: 1885
5h Ziadi A. Martin R. Org. Lett. 2012; 14: 1266
5i Ziadi A. Correa A. Martin R. Chem. Commun. 2013; 49: 4286
5j Ishida N. Nakanishi Y. Murakami M. Angew. Chem. Int. Ed. 2013; 52: 11875
5k Xu T. Dong G. Angew. Chem. Int. Ed. 2012; 51: 7567
5l Xu T. Ko HM. Savage NA. Dong G. J. Am. Chem. Soc. 2012; 134: 20005
5m Xu T. Savage NA. Dong G. Angew. Chem. Int. Ed. 2014; 53: 1891
5n Xu T. Dong G. Angew. Chem. Int. Ed. 2014; 53: 10733
5o Juliá-Hernández F. Ziadi A. Nishimura A. Martin R. Angew. Chem. Int. Ed. 2015; 54: 9537

For radical-mediated examples, see:

6a Rocek J. Radkowsky AE. J. Am. Chem. Soc. 1968; 90: 2986
6b Meyer K. Rocek J. J. Am. Chem. Soc. 1972; 94: 1209
6c Tsunoi S. Ryu I. Tamura Y. Yamasaki S. Sonoda N. Synlett 1994; 1009
6d Casey BM. Eakin CA. Flowers RA. II. Tetrahedron Lett. 2009; 50: 1264
6e Zhao H. Fan X. Yu J. Zhu C. J. Am. Chem. Soc. 2015; 137: 3490
6f Yu J. Zhao H. Liang S. Bao X. Zhu C. Org. Biomol. Chem. 2015; 13: 7924
6g Ren R. Zhao H. Huan L. Zhu C. Angew. Chem. Int. Ed. 2015; 54: 12692
6h Fan X. Zhao H. Yu J. Bao X. Zhu C. Org. Chem. Front. 2016; 3: 227
6i Ren R. Wu Z. Xu Y. Zhu C. Angew. Chem. Int. Ed. 2016; 55: 2866
6j Ren R. Wu Z. Zhu C. Chem. Commun. 2016; 52: 8160
6k Wang D. Ren R. Zhu C. J. Org. Chem. 2016; 81: 8043
6l Huan L. Zhu C. Org. Chem. Front. 2016; 3: 1467
6m Wang M. Wu Z. Zhu C. Org. Chem. Front. 2017; 4: 427

7 Yu J. Yan H. Zhu C. Angew. Chem. Int. Ed. 2016; 55: 1143
8 Ishida N. Sawano S. Murakami M. Nat. Commun. 2014; 5: 3111

9a Ishida N. Sawano S. Masuda Y. Murakami M. J. Am. Chem. Soc. 2012; 134: 17502
9b Li Y. Lin Z. J. Org. Chem. 2013; 78: 11357
9c Ding L. Ishida N. Murakami M. Morokuma K. J. Am. Chem. Soc. 2014; 136: 169
9d Xia Y. Liu Z. Liu Z. Ge R. Ye F. Hossain M. Zhang Y. Wang J. J. Am. Chem. Soc. 2014; 136: 3013
9e Ishida N. Ishikawa N. Sawano S. Masuda Y. Murakami M. Chem. Commun. 2015; 51: 1882
9f Fu X.-F. Xiang Y. Yu Z.-X. Chem. Eur. J. 2015; 21: 4242
9g Zhao C. Liu L.-C. Wang J. Jiang C. Zhang Q.-W. He W. Org. Lett. 2016; 18: 328

10 Ethyl (2E)-3-[2-(2-Oxocyclohexyl)phenyl]acrylate (3); Typical Procedure A flask was charged with RBCB 1 (0.2 mmol, 1 equiv), [{Rh(OH)(cod)}₂] (0.005 mmol, 2.5 mol%), and PPh₃ (0.01 mmol, 5 mol%), and then subjected to three cycles of evacuation and flushing with N₂. Freshly distilled anhyd toluene (2 mL) and ethyl acrylate (0.4 mmol, 2 equiv) were added to the mixture by syringe. The resulting mixture was stirred at rt until the starting material was consumed (TLC). After removal of the solvent, the residue was purified by flash column chromatography (silica gel, EtOAc–PE) to give a yellow solid; yield: 47.8 mg (88%); mp 55–57 °C. FTIR (KBr): 3029, 2933, 2866, 1712, 1681, 1599 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.78 (d, J = 15.6 Hz, 1 H), 7.56 (dd, J = 7.6, 0.8 Hz, 1 H), 7.38 (ddd, J = 7.6, 7.6, 1.2 Hz, 1 H), 7.29 (d, J = 7.6 Hz, 1 H), 7.20 (dd, J = 7.6, 0.8 Hz, 1 H), 6.31 (d, J = 15.6 Hz, 1 H), 4.25 (q, J = 7.2 Hz, 2 H), 3.93 (dd, J = 12.8, 5.6 Hz, 1 H), 2.62–2.48 (m, 2 H), 2.31–2.16 (m, 2 H), 2.10–1.98 (m, 2 H), 1.94–1.79 (m, 2 H), 1.33 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 209.0, 166.4, 141.7, 137.9, 133.2, 129.4, 128.4, 126.8, 126.5, 120.0, 60.1, 53.2, 41.9, 34.4, 27.0, 25.2, 13.8. ESI: m/z = 295.1 [M + Na]⁺. HRMS [ESI]; m/z [M + Na]⁺ calcd for C₁₇H₂₀NaO₃: 295.1310; found: 295.1320.

11a Wessels P. Göhrt A. Zeeck A. Drautz H. Zähner HJ. J. Antibiot. 1991; 44: 1013
11b Onofrey TJ. Gomez D. Winters M. Moore HW. J. Org. Chem. 1997; 62: 5658
11c Kogan NM. Rabinowitz R. Levi P. Gibson D. Sandor P. Schlesinger M. Mechoulam R. J. Med. Chem. 2004; 47: 3800

12a Suzuki S. Hosoe T. Nozawa K. Yaguchi T. Udagawa S. Kawai K.-i. J. Nat. Prod. 1999; 62: 1328
12b Kuo Y.-H. Chen C.-H. Tetrahedron Lett. 2001; 42: 2985
12c Wu C.-C. Peng C.-F. Tsai I.-L. Abd El-Razek MH. Huang H.-S. Chen I.-S. Phytochemistry 2007; 68: 1338
12d Kouam SF. Yapna DB. Krohn K. Ngadjui BT. Ngoupayo J. Choudhary MI. Schulz B. J. Nat. Prod. 2007; 70: 600
12e Geng W.-L. Wang X.-Y. Kurtán T. Mándi A. Tang H. Schulz B. Sun P. Zhang W. J. Nat. Prod. 2012; 75: 1828

Supplementary Material

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