Primary 1,2-Diamine Catalysis (V): Efficient Asymmetric Aldol Reactions of Isatins with Cyclohexanone

Yi Liu; Pengchao Gao; Junfeng Wang; Qi Sun; Zemei Ge; Runtao Li

doi:10.1055/s-0031-1290507

Synlett, Table of Contents

Synlett 2012; 23(7): 1031-1034
DOI: 10.1055/s-0031-1290507

letter

Primary 1,2-Diamine Catalysis (V): Efficient Asymmetric Aldol Reactions of Isatins with Cyclohexanone

Yi Liu

State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmeceutical Science, Peking University, Beijing 100191, P. R. of China, Email: lirt@mail.bjmu.edu.cn Email: sunqi@bjmu.edu.cn

,

Pengchao Gao

State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmeceutical Science, Peking University, Beijing 100191, P. R. of China, Email: lirt@mail.bjmu.edu.cn Email: sunqi@bjmu.edu.cn

,

Junfeng Wang

State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmeceutical Science, Peking University, Beijing 100191, P. R. of China, Email: lirt@mail.bjmu.edu.cn Email: sunqi@bjmu.edu.cn

,

Qi Sun*

State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmeceutical Science, Peking University, Beijing 100191, P. R. of China, Email: lirt@mail.bjmu.edu.cn Email: sunqi@bjmu.edu.cn

,

Zemei Ge

State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmeceutical Science, Peking University, Beijing 100191, P. R. of China, Email: lirt@mail.bjmu.edu.cn Email: sunqi@bjmu.edu.cn

,

Runtao Li*

State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmeceutical Science, Peking University, Beijing 100191, P. R. of China, Email: lirt@mail.bjmu.edu.cn Email: sunqi@bjmu.edu.cn

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Abstract

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Abstract

1,2-Diaminocyclohexane-hexanedioic acid has been demonstrated to catalyze the asymmetric aldol reactions of cycloketones and various isatin derivatives efficiently in MeOH–H₂O. The corresponding products were obtained in good yields (70–90%) with high diastereoselectivity (up to 99:1 anti/syn) and enantioselectivity (up to 99% ee).

Key words

asymmetric aldol reaction - diaminocyclohexane - organocatalyst - isatin

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References

References and Notes

1a Peddibhotla S. Curr. Bioact. Compd. 2009; 5: 20
1b Galliford CV, Scheidt KA. Angew. Chem. Int. Ed. 2007; 46: 8748 ; Angew. Chem. 2007, 119, 8902
1c Marti C, Carreira EM. Eur. J. Org. Chem. 2003; 2209
1d Kamano Y, Zhang H.-P, Ichihara Y, Kizu H, Komiyama K, Pettit GR. Tetrahedron Lett. 1995; 36: 2783
1e Zhang H.-P, Kamano Y, Ichihara Y, Kizu H, Komiyama K, Itokawa H, Pettit GR. Tetrahedron 1995; 51: 5523
1f Tang Y.-Q, Sattler I, Thiericke R, Grabley S. Eur. J. Org. Chem. 2001; 66: 261
1g Hayashi M, Rho M.-C, Enomoto A, Fukami A, Kim Y.-P, Kikuchi Y, Sunazuka T, Hirose T, Komiyama K, Ōmura S. Proc. Natl. Acad. Sci. U.S.A. 2002; 99: 14728
1h Kitajima M, Mori I, Arai K, Kogure N, Takayama H. Tetrahedron Lett. 2006; 47: 3199

2a Kamenecka TM, Danishefsky SJ. Chem. Eur. J. 2001; 7: 41
2b Nicolaou KC, Rao PB, Hao J, Reddy MV, Rassias G, Huang X, Chen DY.-K, Snyder SA. Angew. Chem. Int. Ed. 2003; 42: 1753
2c Liao Y.-J, Wu Y.-L, Chuang C.-P. Tetrahedron 2003; 59: 3511
2d Barroso S, Blay G, Cardona L, Fernandez I, Garcia B, Pedro JR. J. Org. Chem. 2004; 69: 6821
2e Cleghorn LA. T, Cooper IR, Fishwick CW. G, Grigg R, MacLachlan WS, Rasparini M, Sridharan V. J. Organomet. Chem. 2003; 687: 483
2f Schwaebisch D, Tchabanenko K, Adlington RM, Cowley AM, Baldwin JE. Chem. Commun. 2004; 22: 2552
2g Luo S, Mi X, Xu H, Wang PG, Cheng J.-P. J. Org. Chem. 2004; 69: 8413
2h Hamashima Y, Suzuki T, Takano H, Shimura Y, Sodeoka M. J. Am. Chem. Soc. 2005; 127: 10164
2i Toullec PY, Jagt RB. C, De Vries JG, Feringa BL, Minnaard AJ. Org. Lett. 2006; 8: 2715
2j Ishimaru T, Shibata N, Nagai J, Nakamura S, Toru T, Kanemasa S. J. Am. Chem. Soc. 2006; 128: 16488
2k May JP, Patrick BO, Perrin DM. Synlett 2006; 3403
2l Yadav JS, Reddy BV. S, Reddy CS, Krishna AD. Tetrahedron Lett. 2007; 48: 2029
2m Sano D, Nagata K, Itoh T. Org. Lett. 2008; 10: 1593
2n Durbin MJ, Willis MC. Org. Lett. 2008; 10: 1413
2o Kumar CN. S. S. P, Devi CL, Rao VJ, Palaniappan S. Synlett 2008; 2023
2p Jia Y.-X, Hillgren JM, Watson EL, Marsden SP, Kundig EP. Chem. Commun. 2008; 34: 4040
2q Trost BM, O’Boyle BM. Org. Lett. 2008; 10: 1369
2r Lai H, Huang Z, Wu Q, Qin Y. J. Org. Chem. 2009; 74: 283
2s Jia Y.-X, Kundig EP. Angew. Chem. Int. Ed. 2009; 48: 1636
2t Castaldi MP, Troast DM, Porco JA. Org. Lett. 2009; 11: 3362
2u Tsuchikama K, Hashimoto Y, Endo K, Shibata T. Adv. Synth. Catal. 2009; 351: 2850
2v Beaumont S, Pons V, Retailleau P, Dodd RH, Dauban P. Angew. Chem. Int. Ed. 2010; 49: 1634
2w An G, Zhou W, Zhang G, Sun H, Han J, Pan Y. Org. Lett. 2010; 12: 4482
2x Urgaonkar S, Cortese JF, Barker RH, Cromwell M, Serrano AE, Wirth DF, Clardy J, Mazitschek R. Org. Lett. 2010; 12: 3998
2y Kothandaraman P, Rao W, Foo SJ, Chan PW. H. Angew. Chem. Int. Ed. 2010; 49: 4619
2z Zheng K, Yin C, Liu X, Lin L, Feng X. Angew. Chem. Int. Ed. 2011; 50: 2573

3a Corrêa RJ, Garden SJ, Angelici G, Tomasini C. Eur. J. Org. Chem. 2008; 736
3b Angelici G, Corrêa RJ, Garden SJ, Tomasini C. Tetrahedron Lett. 2009; 50: 814

4a Nakamura S, Hara N, Nakashima H, Kubo K, Shibata N, Toru T. Chem. Eur. J. 2008; 14: 8079
4b Hara N, Nakamura S, Shibata N, Toru T. Adv. Synth. Catal. 2010; 352: 1621

5 Chen JR, Liu XP, Zhu XY, Li L, Qiao YF, Zhang JM, Xiao WJ. Tetrahedron 2007; 63: 10437
6 Malkov AV, Kabeshov MA, Bella M, Kysilka O, Malyshev DA, Pluháčková K, Kočovský P. Org. Lett. 2007; 9: 5473
7 Guo Q, Bhanushali M, Zhao CG. Angew. Chem. Int. Ed. 2010; 49: 9460
8 Ricci A, Bernardi L, Gioia C, Vierucci S, Robitzer M, Quignard F. Chem. Commun. 2010; 46: 6288

9a Raj M, Veerasamy N, Singh V. Tetrahedron Lett. 2010; 51: 2157
9b Popp FD, Donigan BE. J. Pharm. Sci. 1979; 68: 519
9c Pajouhesh H, Parson R, Popp FD. J. Pharm. Sci. 1983; 72: 318
9d Joshi KC, Dandia A, Sanan S. J. Fluorine Chem. 1989; 44: 59

10 Wang JF, Qi C, Ge ZM, Cheng TM, Li RT. Chem. Commun. 2010; 46: 2124
11 Wang JF, Wang X, Ge ZM, Cheng TM, Li RT. Chem. Commun. 2010; 46: 1751
12 Liu Y, Wang JF, Sun Q, Li RT. Tetrahedron Lett. 2011; 52: 3584
13 Typical Procedure To the mixed solvent (2 mL, MeOH–H₂O = 1:1) was added the corresponding isatin (0.2 mmol), cyclohexanone (0.6 mmol), and catalyst 13 (0.04 mmol) with equal amount of hexanedioic acid (0.04 mmol). The mixture was stirred at r.t. for 14 h, then quenched with additional H₂O. The organic matter was extracted with EtOAc, dried over Na₂SO₄, and the filtrate was concentrated to get the crude product, which was further purified by a silica gel chromatography. 3-Hydroxy-3-(2-oxocyclohexyl)indolin-2-one (16a) Yield 90%; mp 159 °C; anti/syn = 20:1; 99% ee. ¹H NMR (400 MHz, DMSO-d ₆): δ = 10.16 (s, 1 H), 7.13–7.21 (m, 2 H), 6.75–6.87 (m, 2 H), 5.77 (s, 1 H), 3.07 (dd, J = 12.0, 4.0 Hz, 1 H), 2.53–2.58 (m, 1 H), 2.36–2.53 (m, 1 H), 2.27–2.34 (m, 1 H), 1.58–2.08 (m, 5 H), 1.43–1.50 (m, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 209.8, 179.4, 144.1, 131.5, 129.3, 125.5, 121.5, 110.1, 74.6, 58.1, 42.1, 27.4, 27.3, 25.1. HRMS: m/z calcd for C₁₄H₁₆NO₃ [M + H⁺]: 246.11247; found: 246.11184. The enantiomeric ratio was determined by chiral HPLC with AD-H column (hexane–2-PrOH = 80:20, 1 mL/min)