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

Authors

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

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

Full Text

References

References and Notes

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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)