Citation: Ya-Qing Xu, Shen-Luan Yu, Yan-Yun Li, Zhen-Rong Dong, Jing-Xing Gao. Novel chiral C₂-symmetric multidentate aminophosphine ligands for use in catalytic asymmetric reduction of ketones[J]. Chinese Chemical Letters, ;2013, 24(6): 527-530. shu

Novel chiral C₂-symmetric multidentate aminophosphine ligands for use in catalytic asymmetric reduction of ketones

1.
State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

Corresponding author: Yan-Yun Li,
Received Date: 24 January 2013
Available Online: 14 March 2013

A series of novel chiral C₂-symmetric multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis(o-formylphenyl)phenylphosphane and easily available monoprotected (1R,2R)-diaminocyclohexane. The catalytic properties of these ligands were investigated in Ir-catalyzed asymmetric transfer hydrogenation of various aromatic ketones, giving the corresponding optical active alcohols with up to 98% conversion and good ee under mild reaction conditions.
- Asymmetric catalysis,
- Iridium,
- Aromatic ketones,
- Aminophosphine ligands,
- Asymmetric transfer hydrogenation
1. [1]
  [1] T. Hamada, T. Torii, K. Izawa, T. Ikariya, A practical synthesis of optically active aromatic epoxides via asymmetric transfer hydrogenation of α-chlorinated ketones with chiral rhodium-diamine catalyst, Tetrahedron 60 (2004) 7411-7417.
2. [2]
  [2] T. Ikariya, A.J. Blacker, Asymmetric transfer hydrogenation of ketones with bifunctional transition metal-based molecular catalysts, Acc. Chem. Res. 40 (2007) 1300-1308.
3. [3]
  [3] R.H. Morris, Asymmetric hydrogenation, transfer hydrogenation and hydrosilylation of ketones catalyzed by iron complexes, Chem. Soc. Rev. 38 (2009) 2282-2291.
4. [4]
  [4] R. Malacea, R. Poli, E. Manoury, Asymmetric hydrosilylation, transfer hydrogenation and hydrogenation of ketones catalyzed by iridium complexes, Coord. Chem. Rev. 254 (2010) 729-752.
5. [5]
  [5] R. Noyori, S. Hashiguchi, Asymmetric transfer hydrogenation catalyzed by chiral ruthenium complexes, Acc. Chem. Res. 30 (1997) 97-102.
6. [6]
  [6] J.X. Gao, T. Ikariya, R. Noyori, A ruthenium(Ⅱ) complex with a C₂-symmetric diphosphine/diamine tetradentate ligand for asymmetric transfer hydrogenation of aromatic ketones, Organometallics 15 (1996) 1087-1089.
7. [7]
  [7] C. Wang, X.F. Wu, J.L. Xiao, Broader, greener, and more efficient: recent advances in asymmetric transfer hydrogenation, Chem. Asian J. 3 (2008) 1750-1770.
8. [8]
  [8] V.A. Pavlov, C2 and C1 symmetry of chiral auxiliaries in catalytic reactions on metal complexes, Tetrahedron 64 (2008) 1147-1179.
9. [9]
  [9] J. Vá clavík, P. Kačer, M. Kuzma, L. Č ervenŷ, Opportunities offered by chiral η⁶-aren;e/N-arylsulfonyldiamine-Ru^Ⅱ catalysts in the asymmetric transfer hydrogenation of ketones and imines, Molecules 16 (2011) 5460-5495.
10. [10]
  [10] S.L. Yu, Y.Y. Li, Z.R. Dong, et al., Synthesis of novel chiral N, P-containing multidentate ligands and their applications in asymmetric transfer hydrogenation, Chin. Chem. Lett. 22 (2011) 1269-1272.
11. [11]
  [11] Z.R. Dong, Y.Y. Li, S.L. Yu, G.S. Sun, J.X. Gao, Asymmetric transfer hydrogenation of ketones catalyzed by nickel complex with new PNO-type ligands, Chin. Chem. Lett. 23 (2012) 533-536.
12. [12]
  [12] S.L. Yu, W.Y. Shen, Y.Y. Li, et al., Iron-catalyzed highly enantioselective reduction of aromatic ketones with chiral P2N4-type macrocycles, Adv. Synth. Catal. 354 (2012) 818-822.
13. [13]
  [13] C. Rancurel, N. Daro, O.B. Borobia, E. Herdtweck, J.P. Sutter, H₂O as a chemical link for ferromagnetic interactions between aminoxyl units, Eur. J. Org. Chem. (2003) 167-171.
14. [14]
  [14] P. Lagriffoule, P. Wittung, M. Eriksson, et al., Peptide nucleic acids with a conformationally constrained chiral cyclohexyl-derived backbone, Chem. Eur. J. 3 (1997) 912-919.
15. [15]
  [15] Compound 2: [α]_D²⁰ +32.8 (c 0.4, CH₂C_l2); ¹H NMR (500 MHz, CDC_l3): δ 4.65 (d, 1H, J = 8.0 Hz, NH carbamate), 3.28-3.05 (m, 1H, CHN), 2.36 (dt, 1H, J = 10.0 Hz and 3.5 Hz, CHN), 2.05-1.95 (m, 2H, CH₂, cycl), 1.78-1.65 (m, 4H, CH₂, cycl and NH₂), 1.45 (s, 9H, tBoc), 1.38-1.05 (m, 4H, 2CH₂, cycl). Compound 3: mp 114-116 ℃; [α]_D²⁰ +53.5 (c 0.2, CH₂C_l2); ¹H NMR (500 MHz, CDC_l3): δ 8.79 (s, 1H), 8.76 (s, 1H), 8.02 (s, 1H), 7.94 (s, 1H), 7.68-7.56 (m, 1H), 7.40-7.18 (m, 10H), 6.90-6.77 (m, 2H), 3.58-3.42 (m, 2H), 2.94-2.77 (m, 2H), 2.23-2.08 (m, 2H), 2.08-1.95 (m, 2H), 1.75-1.62 (m, 4H), 1.50-1.42 (m, 4H), 1.34 (s, 18H), 1.25-1.16 (m, 4H); ¹³C NMR (125 MHz, CDC_l3): δ 159.0, 158.8, 155.3, 139.8 (d, J = 18.8 Hz), 139.3 (d, J = 17.5 Hz), 136.4 (d, J = 16.3 Hz), 136.2, 134.4, 134.2, 133.7, 133.4, 130.3, 130.2, 129.1, 128.9, 128.7, 128.6, 128.2, 78.8, 73.9, 54.3, 33.2, 33.0, 31.8, 28.4, 24.9, 24.8, 24.0
16. [16]
  (d); ³¹P NMR ((202 MHz, CDC_l3): δ 20.55; HRMS (ESI, m/z) Calcd. for C₄₂H₅₆N₄O₄P [M⁺H]+: 711.4034, found: 711.4034. Compound 4: mp 134-136 ℃; [α]_D²⁰ 7.0 (c 0.2, CH₂C_l2); ¹H NMR (500 MHz, CDC_l3): δ 7.62-7.45 (m, 2H), 7.43-7.30 (m, 5H), 7.29-7.20 (m, 2H), 7.20-7.18 (m, 2H), 6.87-6.72 (m, 2H), 5.05-4.42 (br m, 2H), 4.08-3.82 (m, 4H), 3.35-3.11 (m, 2H), 2.26-2.14 (m, 2 H), 2.10-2.00 (m, 2H), 1.98-1.85 (m, 4H), 1.69-1.56 (m, 4H), 1.44 (s, 18 H), 1.30-1.21 (m, 2 H), 1.13-0.98 (m, 6 H); ¹³C NMR (125 MHz, CDC_l3): δ 156.1, 145.0, 135.0, 134.3, 134.1, 133.6, 133.4, 129.1, 129.0, 128.9, 128.7, 128.6, 127.2, 60.6, 60.4, 54.6, 49.3, 49.2, 49.1, 49.0, 32.7, 32.6, 31.6, 28.4, 24.7, 24.5; ³¹P NMR ((202 MHz, CDC_l3): δ 25.35; HRMS (ESI, m/z) Calcd. for C₄₂H₆0N₄O₄P [M⁺H]+: 715.4347, found: 715.4345. Compound 5: mp 60-62 ℃; [α]_D²⁰ 37.0 (c 0.2, CH₂C_l2); ¹H NMR (400 MHz, CDC_l3): δ 7.58-7.36 (m, 3H), 7.35-7.28 (m, 4H), 7.26-7.13 (m, 4H), 6.92-6.75 (m, 2H), 4.12-3.73 (m, 4H), 3.25 (br s, 6H), 2.46-2.28 (m, 2H), 2.28-2.00 (m, 4H), 1.98-1.84 (m, 2H), 1.75-1.60 (m, 4H), 1.28-1.12 (m, 6H), 1.03-0.82 (m, 2H); ¹³C NMR (100 MHz, CDC_l3): δ 144.5 (d, J = 32 Hz), 144.2 (d, J = 31 Hz), 136.4 (d, J = 7 Hz), 135.6 (d, J = 12 Hz), 135.4 (d, J = 11 Hz), 134.4, 134.2, 134.0, 133.8, 129.8 (d, J = 5 Hz), 129.3, 128.9, 128.7 (d, J = 7 Hz), 127.7 (d, J = 12 Hz), 61.9 (d, J = 17 Hz), 55.1 (d, J = 17 Hz), 50.0, 49.8, 49.4, 49.3, 33.8, 33.4, 31.2, 31.1, 25.1
17. [17]
  (d), 24.8
18. [18]
  (d). ³¹P NMR ((162 MHz, CDC_l3): δ 24.80; HRMS (ESI, m/z) Calcd. for C₃₂H₄₄N₄P [M⁺H]+: 515.3298, found: 515.3303.
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Novel chiral C2-symmetric multidentate aminophosphine ligands for use in catalytic asymmetric reduction of ketones

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通讯作者: 陈斌, bchen63@163.com

Novel chiral C₂-symmetric multidentate aminophosphine ligands for use in catalytic asymmetric reduction of ketones