Asymmetric Organocatalytic Michael/Michael/Henry Sequence to Construct Cyclohexanes with Six Vicinal Stereogenic Centers

Yushuang Chen; Xiaohua Liu; Weiwei Luo; Lili Lin; Xiaoming Feng

doi:10.1055/s-0036-1588940

Synlett, Inhaltsverzeichnis

Synlett 2017; 28(08): 966-969
DOI: 10.1055/s-0036-1588940

letter

Asymmetric Organocatalytic Michael/Michael/Henry Sequence to Construct Cyclohexanes with Six Vicinal Stereogenic Centers

Yushuang Chen

Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China eMail: liuxh@scu.edu.cn

,

Xiaohua Liu*

Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China eMail: liuxh@scu.edu.cn

,

Weiwei Luo

Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China eMail: liuxh@scu.edu.cn

,

Lili Lin

Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China eMail: liuxh@scu.edu.cn

,

Xiaoming Feng

Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China eMail: liuxh@scu.edu.cn

› Institutsangaben

Abstract

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Abstract

An efficient, asymmetric, catalytic, triple-cascade reaction between α-keto esters and nitroalkenes to construct cyclohexanes with six vicinal stereogenic centers in good yields and with high enantioselectivities has been established. A bifunctional guanidine–amide organocatalyst proved to be useful for the Michael/Michael/Henry sequence through Brønsted base and hydrogen-bonding cooperative catalysis.

Key words

asymmetric catalysis - cascade reaction - cyclohexanes - organocatalysis - keto esters - nitroalkenes

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Referenzen

References and Notes

For reviews on asymmetric organocatalysis, see:

1a Bertelsen S, Jørgensen KA. Chem. Soc. Rev. 2009; 38: 2178
1b Palomo C, Oiarbide M, López R. Chem. Soc. Rev. 2009; 38: 632
1c Dondoni A, Massi A. Angew. Chem. Int. Ed. 2008; 47: 4638
1d Moyano A, Rios R. Chem. Rev. 2011; 111: 4703
1e Chauhan P, Mahajan S, Kaya U, Hack D, Enders D. Adv. Synth. Catal. 2015; 357: 253
1f Pellissier H. Tetrahedron. 2016; 72: 3133
1g Dalko PI, Moisan L. Angew. Chem. Int. Ed. 2004; 43: 5138
1h Barbas CF. III. Angew. Chem. Int. Ed. 2008; 47: 42
1i MacMillan DW. C. Nature 2008; 455: 304
1j Giacalone F, Gruttadauria M, Agrigento P, Noto R. Chem. Soc. Rev. 2012; 41: 2406
1k Borissov A, Davies TQ, Ellis SR, Fleming TA, Richardson MS. W, Dixon DJ. Chem. Soc. Rev. 2016; 45: 5474

2a Grondal C, Jeanty M, Enders D. Nat. Chem. 2010; 2: 167
2b Pellissier H. Adv. Synth. Catal. 2012; 354: 237
2c Volla CM. R, Atodiresei I, Rueping M. Chem. Rev. 2014; 114: 2390
2d Enders D, Grondal C, Hüttl MR. M. Angew. Chem. Int. Ed. 2007; 46: 1570
2e Albrecht L, Jiang H, Jørgensen KA. Angew. Chem. Int. Ed. 2011; 50: 8492
2f Guo H.-C, Ma J.-A. Angew. Chem. Int. Ed. 2006; 45: 354
2g Bonne D, Constantieux T, Coquerel Y, Rodriguez J. Org. Biomol. Chem. 2012; 10: 3969
2h Ramón DJ, Yus M. Angew. Chem. Int. Ed. 2005; 44: 1602

3a Xu L.-W, Luo J, Lu Y. Chem. Commun. 2009; 1807
3b Yu X.-H, Wang W. Org. Biomol. Chem. 2008; 6: 2037
3c Marson CM. Chem. Soc. Rev. 2012; 41: 7712
3d Melchiorre P, Marigo M, Carlone A, Bartoli G. Angew. Chem. Int. Ed. 2008; 47: 6138
3e List B. Chem. Commun. 2006; 819
3f Palomo C, Mielgo A. Angew. Chem. Int. Ed. 2006; 45: 7876
3g Jensen KL, Dickmeiss G, Jiang H, Albrecht Ł, Jørgensen KA. Acc. Chem. Res. 2012; 45: 248
3h Nielsen M, Worgull D, Zweifel T, Gschwend B, Bertelsen S, Jørgensen KA. Chem. Commun. 2011; 47: 632
3i Li J.-L, Liu T.-Y, Chen Y.-C. Acc. Chem. Res. 2012; 45: 1491

4a Taylor MS, Jacobsen EN. Angew. Chem. Int. Ed. 2006; 45: 1520
4b Grossmann A, Enders D. Angew. Chem. Int. Ed. 2012; 51: 314
4c Fèvre M, Pinaud J, Gnanou Y, Vignolle J, Taton D. Chem. Soc. Rev. 2013; 42: 2142
4d Bugaut X, Glorius F. Chem. Soc. Rev. 2012; 41: 3511
4e Nair V, Vellalath S, Babu BP. Chem. Soc. Rev. 2008; 37: 2691
4f Flanigan DM, Romanov-Michailidis F, White NA, Rovis T. Chem. Rev. 2015; 115: 9307
4g Hopkinson MN, Richter C, Schedler M, Glorius F. Nature. 2014; 510: 485

5a Siau W.-Y, Wang J. Catal. Sci. Technol. 2011; 1: 1298
5b Wang Y, Lu H, Xu P.-F. Acc. Chem. Res. 2015; 48: 1832

6a Enders D, Wang C, Mukanova M, Greb A. Chem. Commun. 2010; 46: 2447
6b Enders D, Urbanietz G, Cassens-Sasse E, Keeß S, Raabe G. Adv. Synth. Catal. 2012; 354: 1481
6c Hong B.-C, Dange NS, Ding C.-F, Liao J.-H. Org. Lett. 2012; 14: 448
6d Hong B.-C, Lin C.-W, Liao W.-K, Lee G.-H. Org. Lett. 2013; 15: 6258
6e Chauhan P, Mahajan S, Loh CC. J, Raabe G, Enders D. Org. Lett. 2014; 16: 2954
6f Chang Y.-P, Gurubrahamam R, Chen K. Org. Lett. 2015; 17: 2908
6g Raja A, Hong B.-C, Liao J.-H, Lee G.-H. Org. Lett. 2016; 18: 1760
6h Hayashi Y, Okano T, Aratake S, Hazelard D. Angew. Chem. Int. Ed. 2007; 46: 4922
6i Tan B, Chua PJ, Li YX, Zhong GF. Org. Lett. 2008; 10: 2437
6j Varga S, Jakab G, Drahos L, Holczbauer T, Czugler M, Soós T. Org. Lett. 2011; 13: 5416
6k Anwar S, Chang H.-J, Chen K. Org. Lett. 2011; 13: 2200
6l Mao ZF, Jia YM, Xu ZQ, Wang R. Adv. Synth. Catal. 2012; 354: 1401
6m Baslé O, Raimondi W, del Mar Sanchez Duque M, Bonne D, Constantieux T, Rodriguez J. Org. Lett. 2010; 12: 5246

7a Shi D, Xie Y, Zhou H, Xia C, Huang HM. Angew. Chem. Int. Ed. 2012; 51: 1248
7b Nakamura A, Lectard S, Shimizu R, Hamashima Y, Sodeoka M. Tetrahedron: Asymmetry 2010; 21: 1682

8a Yu ZP, Liu XH, Zhou L, Lin LL, Feng XM. Angew. Chem. Int. Ed. 2009; 48: 5195
8b Dong SX, Liu XH, Chen XH, Mei F, Zhang YL, Gao B, Lin LL, Feng XM. J. Am. Chem. Soc. 2010; 132: 10650
8c Dong SX, Liu XH, Zhang YL, Lin LL, Feng XM. Org. Lett. 2011; 13: 5060
8d Chen XH, Dong SX, Qiao Z, Zhu Y, Xie MS, Lin LL, Liu XH, Feng XM. Chem. Eur. J. 2011; 17: 2583
8e Yang Y, Dong SX, Liu XH, Lin LL, Feng XM. Chem. Commun. 2012; 48: 5040
8f Xiao X, Liu XH, Dong SX, Cai YF, Lin LL, Feng XM. Chem. Eur. J. 2012; 18: 15922
8g Dong SX, Liu XH, Zhu Y, He P, Lin LL, Feng XM. J. Am. Chem. Soc. 2013; 135: 10026

9 Hexasubstituted Cyclohexanes 3aa–3ik; General Procedure Guanidine G-5 (10 mol%), α-keto ester 1 (0.1 mmol), and 4 Å MS (20 mg) were weighed into a test tube under N₂. THF (0.5 mL) was added and the solution was stirred for 0.5 h at 0 °C. Nitroalkene 2 (0.3 mmol) was then added at 0 °C, and the resulting mixture was stirred for 3 d at 0 °C to give the product 3, which was purified by flash chromatography.
10 tert-Butyl (1R,2R,3R,4S,5R,6S)-2-Benzyl-1-hydroxy-4,6-dinitro-3,5-diphenylcyclohexanecarboxylate (3aa) White solid; yield: 51.7 mg (93%, 90% ee, >20:1 dr); mp 162 °C; [α]_D ²⁹ +45.3 (c 0.47, CH₂Cl₂); HPLC: [Daicel CHIRALCEL IA; hexane–i-PrOH (85:15); flow rate = 1.0 mL/min; λ = 210 nm]: t _R = 7.33 min (minor), 12.59 min (major). ¹H NMR (400 MHz, CDCl₃): δ = 7.35–7.08 (m, 13 H), 6.78 (d, J = 7.2 Hz, 2 H), 5.22–5.16 (m, 1 H), 5.10 (dd, J = 12.4, 6.4 Hz, 1 H), 4.49 (t, J = 12.4 Hz, 1 H), 4.18 (s, 1 H), 3.54 (t, J = 6.4 Hz, 1 H), 2.95 (s, 1 H), 2.54–2.36 (m, 2 H), 1.59 (s, 9 H). ¹³C NMR (100 MHz, CDCl₃): δ = 171.5, 137.4, 134.9, 132.1, 129.0, 128.9, 128.6, 128.5, 128.4, 128.3 127.0, 92.7, 90.3, 86.6, 77.7, 47.1, 45.7, 40.3, 33.7, 27.9. HRMS (ESI-TOF): m/z [M + Na]⁺ calcd for C₃₀H₃₂N₂NaO₇ ⁺: 555.2102; found: 555.2101. tert-Butyl (1R,2R,3R,4S,5R,6S)-2-Benzyl-1-hydroxy-4,6-dinitro-3,5-bis(2-tolyl)cyclohexanecarboxylate (3ah) White solid; yield: 53.0 mg (91%, 95% ee, >20:1 dr); mp 140 °C; [α]_D ²⁶ +72.6 (c 1.26, CH₂Cl₂); HPLC: [Daicel CHIRALCEL IA; hexane–i-PrOH (85:15); flow rate = 1.0 mL/min; λ = 210 nm]: t _R = 10.21 min (minor), 16.58 min (major). ¹H NMR (400 MHz, CDCl₃): δ = 8.53 (d, J = 7.6 Hz, 1 H), 7.33 (d, J = 7.6 Hz, 1 H), 7.24–7.08 (m, 8 H), 6.97 (d, J = 7.6 Hz, 1 H), 6.74 (d, J = 6.0 Hz, 2 H), 5.27 (t, J = 12.0 Hz, 2 H), 4.88 (t, J = 12.0 Hz, 1 H), 4.35 (s, 1 H), 4.16 (t, J = 6.4 Hz, 1 H), 3.26 (s, 1 H), 2.65–2.53 (m, 1 H), 2.50 (s, 3 H), 2.49–2.32 (m, 1 H), 1.64 (s, 9 H), 1.32 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 171.6, 140.0, 139.3, 137.0, 133.2, 131.7, 131.3, 131.2, 131.1, 129.0, 128.8, 128.1, 128.0, 126.9, 126.3, 126.2, 124.0, 93.1, 90.8, 86.5, 77.8, 45.2, 39.8, 34.8, 33.5, 27.9, 19.5, 19.3. HRMS (ESI-TOF): m/z [M + Na]⁺ calcd for C₃₂H₃₆N₂NaO₇ ⁺ : 583.2415; found: 583.2415.