Synlett 2016; 27(04): 586-590
DOI: 10.1055/s-0035-1560485
cluster
© Georg Thieme Verlag Stuttgart · New York

Enantioselective Synthesis of Tetrahydroindolizines via Ruthenium–Chiral Phosphoric Acid Sequential Catalysis

Yong Zhou
a  State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China   eMail: slyou@sioc.ac.cn
b  School of Pharmacy, East China University of Science and Technology, 130 Mei-Long Road, Shanghai 200237, P. R. of China
,
Xiao-Wei Liu
a  State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China   eMail: slyou@sioc.ac.cn
,
Qing Gu
a  State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China   eMail: slyou@sioc.ac.cn
,
Shu-Li You*
a  State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China   eMail: slyou@sioc.ac.cn
b  School of Pharmacy, East China University of Science and Technology, 130 Mei-Long Road, Shanghai 200237, P. R. of China
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Publikationsverlauf

Received: 29. Juni 2015

Accepted after revision: 04. September 2015

Publikationsdatum:
01. Oktober 2015 (online)


Abstract

A chiral phosphoric acid and a ruthenium complex were found to catalyze an olefin cross-metathesis–asymmetric intramolecular Friedel–Crafts alkylation of N-tethered olefin pyrroles and conjugated enones to provide a variety of chiral tetrahydroindolizine derivatives in moderate to good yields and enantioselectivity (up to 93% ee).

Supporting Information

 
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  • 10 See the Supporting Information for details.
  • 11 Typical Procedure for the Sequential Catalysis A flame-dried Schlenk tube was cooled to r.t. To a solution of olefin pyrrole 2a (42.2 mg, 0.20 mmol, 1.0 equiv) in toluene (2 mL) was added enone 3a (31.7 mg, 1.2 equiv) and 3 Å MS (50 mg), then chiral phosphoric acid (S)-1f (7.0 mg, 0.01 mmol, 5 mol%) and Zhan-1B (7.3 mg, 0.01 mmol, 5 mol%) were added in one portion. The reaction was stirred at r.t. After the reaction was complete (monitored by TLC), it was quenched with sat. NaHCO3 solution and extracted with EtOAc. The organic layers were washed with brine, dried over anhydrous Na2SO4, and filtered. After the solvent was removed in vacuo, the crude product was purified by neutral Al2O3 column chromatography (PE–EtOAc, 30:1 to 20:1) to afford product 4aa. Yellow oil, 42.8 mg, 70% yield, 88% ee [Daicel Chiralcel OD-H (0.46 cm × 25 cm), n-hexane–2-PrOH, 95:5, v = 0.5 mL min–1, λ = 254 nm, t R (minor) = 41.34 min, t R (major) = 30.02 min]; [α]D 25 –42.6 (c 0.65, CHCl3). 1H NMR (300 MHz, CDCl3): δ = 8.04 (d, J = 7.2 Hz, 2 H), 7.63–7.58 (m, 1 H), 7.53–7.48 (m, 2 H), 7.44–7.37 (m, 4 H), 7.32–7.26 (m, 1 H), 6.24 (d, J = 3.3 Hz, 1 H), 6.05 (d, J = 3.9 Hz, 1 H), 4.07–4.00 (m, 1 H), 3.95–3.86 (m, 1 H), 3.75–3.66 (m, 1 H), 3.56 (dd, J = 16.8, 4.5 Hz, 1 H), 3.27 (dd, J = 16.5, 8.7 Hz, 1 H), 2.23–2.15 (m, 1 H), 2.08–1.84 (m, 2 H), 1.56–1.44 (m, 1 H). 13C NMR (75 MHz, CDCl3): δ = 199.2, 137.4, 134.0, 133.8, 133.4, 133.2, 128.9, 128.5, 128.4, 126.7, 108.4, 104.5, 45.3, 45.1, 31.1, 27.6, 23.1. IR (thin film): νmax = 3059, 2925, 2864, 1680, 1597, 1505, 1472, 1445, 1414, 1356, 1306, 1278, 1204, 1180, 1074, 1023, 995, 916, 801, 748, 692, 622 cm–1. ESI-HRMS: m/z calcd for C22H22NO [M + H]+: 316.1696; found: 316.1696.