Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml
Synthesis 2018; 50(08): 1661-1666
DOI: 10.1055/s-0036-1591751
DOI: 10.1055/s-0036-1591751
paper
Enantioselective Construction of Bridgehead Quaternary Carbon Containing Bicyclo[3.3.1]nonanes by Palladium-Catalyzed Desymmetric Arylation
This work was financially supported by National Natural Science Foundation of China (NSFC 21772148, 21602160).Further Information
Publication History
Received: 05 December 2017
Accepted: 12 December 2017
Publication Date:
24 January 2018 (online)
![](https://www.thieme-connect.de/media/synthesis/201808/lookinside/thumbnails/ss-2017-h0783-op_10-1055_s-0036-1591751-1.jpg)
Abstract
An enantioselective and catalytic method for the synthesis of bridgehead quaternary carbon containing bicyclo[3.3.1]nonanes is described. The intramolecular desymmetric arylation of α-disubstituted 1,3-diketones was achieved using a chiral Pd/PHOX complex. A variety of bridged cyclic molecules, common skeleton for polyprenylated acylphloroglucinols, were obtained in up to 84% yield with 86% ee.
Key words
asymmetric catalysis - desymmetrization - all-carbon quaternary center - palladium - arylation - bicyclic compoundSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1591751.
- Supporting Information
-
References
- 1a Douglas CJ. Overman LE. Proc. Natl. Acad. Sci. U.S.A. 2003; 100: 5363
- 1b Quasdorf KW. Overman LE. Nature 2014; 516: 181
- 1c Ling T. Rivas F. Tetrahedron 2016; 72: 6729
- 1d Oliver S. Evans PA. Synthesis 2013; 45: 3179
- 1e Liu Y. Han SJ. Liu WB. Stoltz BM. Acc. Chem. Res. 2015; 48: 740 ; and references cited therein
- 2a Richard J.-A. Pouwer RH. Chen DY.-K. Angew. Chem. Int. Ed. 2012; 51: 4536
- 2b Singh IP. Sidana J. Bharate SB. Foley WJ. Nat. Prod. Rep. 2010; 27: 393
- 2c Ciochina R. Grossman RB. Chem. Rev. 2006; 106: 3963
- 3a Simpkins NS. Chem. Commun. 2013; 49: 1042
- 3b Peters JA. Synthesis 1979; 321
- 3c Butkus E. Synlett 2001; 1827
- 3d Momose T. Takizawa S. Kirihara M. Synth. Commun. 1997; 27: 3313
- 4a Butkus E. Stonèius A. Synlett 1999; 234
- 4b Zhao W. Chem. Rev. 2010; 110: 1706
- 4c Rodeschini V. Ahmad NM. Simpkins NS. Org. Lett. 2006; 8: 5283
- 4d Takagi R. Inoue Y. Ohkata K. J. Org. Chem. 2008; 73: 9320
- 4e Mitasev B. Porco JA. Jr. Org. Lett. 2009; 11: 2285
- 4f Siegel DR. Danishefsky SJ. J. Am. Chem. Soc. 2006; 128: 1048
- 4g Ting CP. Maimone TJ. J. Am. Chem. Soc. 2015; 137: 10516
- 4h Abe M. Saito A. Nakada M. Tetrahedron Lett. 2010; 51: 1298
- 4i Zhang Q. Porco JA. Jr. Org. Lett. 2012; 14: 1796
- 4j Sparling BA. Moebius DC. Shair MD. J. Am. Chem. Soc. 2013; 135: 644
- 4k Li ZN. Lam SM. Ip I. Wong WT. Chiu P. Org. Lett. 2017; 19: 4464
- 4l Promontorio R. Richard JA. Marson CM. RSC Adv. 2016; 6: 114412
- 5a Rueping M. Kuenkel A. Tato F. Bats JW. Angew. Chem. Int. Ed. 2009; 48: 3699
- 5b Cao C.-L. Sun X.-L. Kang Y.-B. Tang Y. Org. Lett. 2007; 9: 4151
- 5c Zhang C. Hu X.-H. Wang Y.-H. Zheng Z. Xu J. Hu X.-P. J. Am. Chem. Soc. 2012; 134: 9585
- 5d Uetake Y. Uwamori M. Nakada M. J. Org. Chem. 2015; 80: 1735
- 5e Gammack Yamagata AD. Datta S. Jackson KE. Stegbauer L. Paton RS. Dixon DJ. Angew. Chem. Int. Ed. 2015; 54: 4899
- 5f Burns AR. Madec AG. E. Low DW. Roy ID. Lam HW. Chem. Sci. 2015; 6: 3550
- 5g Presset M. Coquerel Y. Rodriguez J. ChemCatChem 2012; 4: 172
- 5h Lefranc A. Gremaud L. Alexakis A. Org. Lett. 2014; 16: 5242
- 6 Liu R.-R. Li B.-L. Lu J. Shen C. Gao J.-R. Jia Y.-X. J. Am. Chem. Soc. 2016; 138: 5198
- 7a Muratake H. Natsume M. Tetrahedron Lett. 1997; 38: 7581
- 7b Muratake H. Natsume M. Nakai H. Tetrahedron 2004; 60: 11783
- 7c Powell NA. Hagen TJ. Ciske FL. Cai C. Duran JE. Holsworth DD. Leonard D. Kennedy RM. Edmunds JJ. Tetrahedron Lett. 2010; 51: 4441
- 7d Iwama T. Rawal VH. Org. Lett. 2006; 8: 5725
- 7e Bellina F. Rossi R. Chem. Rev. 2009; 110: 1082
- 7f Johansson CC. C. Colacot TJ. Angew. Chem. Int. Ed. 2010; 49: 676
- 7g Burtoloso AC. B. Synlett 2009; 320
- 7h Zhou J. Synlett 2012; 23: 1
- 8 For a review on asymmetric desymmetrization, see: García-Urdiales E. Alfonso I. Gotor V. Chem. Rev. 2005; 105: 313
- 9 During the preparation of our manuscript, Shi and co-workers reported a similar strategy using Pd(OAc)2/FOXAP complex as catalyst, see: Zhu C. Wang D. Zhao Y. Sun W.-Y. Shi Z. J. Am. Chem. Soc. 2017; 139: 16486
- 10a Liu W.-B. He H. Dai L.-X. You S.-L. Synthesis 2009; 2076
- 10b Liu W.-B. Zheng C. Zhuo C.-X. Dai L.-X. You S.-L. J. Am. Chem. Soc. 2012; 134: 4812
- 11a Helmchen G. Pfaltz A. Acc. Chem. Res. 2000; 33: 336
- 11b Tani K. Behenna DC. McFadden RM. Stoltz BM. Org. Lett. 2007; 9: 2529
- 12a Wu W. You C. Yin C. Liu Y. Dong X.-Q. Zhang X. Org. Lett. 2017; 19: 2548
- 12b Wu W. Liu S. Duan M. Tan X. Chen C. Xie Y. Lan Y. Dong X.-Q. Zhang X. Org. Lett. 2016; 18: 2938
- 13a Mei T.-S. Patel HH. Sigman MS. Nature 2014; 508: 340
- 13b Kikushima K. Holder JC. Gatti M. Stoltz BM. J. Am. Chem. Soc. 2011; 133: 6902
- 13c Kadam AA. Ellern A. Stanley LM. Org. Lett. 2017; 19: 4062
- 14 No desired arylation product was observed on treatment of 2-(2-bromobenzyl)-2-phenylcyclohexane-1,3-dione under the standard conditions.
- 15 Enantiopure 2j was obtained by single recrystallization from i-PrOH/hexane.
- 16 CCDC 1589080 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
For selected examples of intramolecular arylation of aliphatic ketones, see:
For selected reviews of asymmetric arylation of carbonyls, see:
For selected examples for construction of chiral quaternary carbon using Pd/L7, see: