Synlett 2016; 27(07): 1047-1050
DOI: 10.1055/s-0035-1561403
cluster
© Georg Thieme Verlag Stuttgart · New York

Anion-Stoichiometry-Dependent Selectivity Enhancement in Ion-Paired Chiral Ligand–Palladium Complex Catalyzed Enantioselective Allylic Alkylation

Kohsuke Ohmatsu
a  Institute of Transformative Bio-Molecules (WPI-ITbM), and Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8601, Japan   Email: tooi@apchem.nagoya-u.ac.jp
,
Yoshiyuki Hara
a  Institute of Transformative Bio-Molecules (WPI-ITbM), and Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8601, Japan   Email: tooi@apchem.nagoya-u.ac.jp
,
Yuya Kusano
a  Institute of Transformative Bio-Molecules (WPI-ITbM), and Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8601, Japan   Email: tooi@apchem.nagoya-u.ac.jp
,
Takashi Ooi*
a  Institute of Transformative Bio-Molecules (WPI-ITbM), and Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8601, Japan   Email: tooi@apchem.nagoya-u.ac.jp
b  CREST, Japan Science and Technology Agency (JST), Nagoya 464-8601, Japan
› Author Affiliations
Further Information

Publication History

Received: 30 January 2016

Accepted: 17 February 2016

Publication Date:
07 March 2016 (online)


Abstract

The ratio of chiral Brønsted acid to ammonium–phosphine hybrid ligand in the in situ preparation of ion-paired chiral ligands was found to have a notable effect on the stereocontrolling ability of the corresponding palladium complex. The use of supramolecular palladium complexes generated from palladium metal, ammonium phosphine, and a chiral phosphoric acid in a ratio of 1:2:3 enabled an excellent level of enantiocontrol in the catalytic asymmetric allylation of α-nitrocarboxylates with a functionalized allylic carbonate.

Supporting Information

 
  • References and Notes

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  • 11 General Procedure for Asymmetric Allylation of Nitroester with Allylic Carbonate To a Schlenk flask were added Pd2(dba)3·CHCl3 (1.29 mg, 1.25 μmol), ammonium phosphine 1·HSO4 (2.8 mg, 5 μmol), chiral phosphoric acid 2b (5.1 mg, 7.5 μmol), and K2CO3 (1.4 mg, 0.010 mmol). The flask was degassed by alternating vacuum evacuation/Ar backfill. After the addition of toluene (1.0 mL), the resulting catalyst mixture was evacuated and refilled with Ar three times. The reaction flask was then warmed up to 30 °C, and nitroester 4a (25.1 mg, 0.10 mmol) and allylic carbonate 5 (30.2 mg, 0.12 mmol) were successively introduced. After stirring for 24 h at the same temperature, the reaction mixture was cooled to r.t. Filtration through the short silica gel pad with the aid of EtOAc and concentration of the filtrate were performed. The reaction mixture was purified by column chromatography on silica gel (hexane–EtOAc = 20:1 as eluent) to afford 6a (38.4 mg, 0.099 mmol, 99% yield, 98% ee) as a colorless liquid. Compound 6a: [α]D 24 –3.08 (c 1.0, CH3OH) for 99% ee. 1H NMR (400 MHz, CDCl3): δ = 7.34 (2 H, t, J = 2.3 Hz), 7.35–7.30 (3 H, m), 7.13 (1 H, dt, J = 15.2, 7.6 Hz), 7.16–7.11 (2 H, m), 6.64 (1 H, dt, J = 15.2, 1.5 Hz), 6.34 (2 H, t, J = 2.3 Hz), 3.65 (1 H, d, J = 14.4 Hz), 3.50 (1 H, d, J = 14.4 Hz), 3.03 (1 H, ddd, J = 15.5, 7.6, 1.5 Hz), 2.99 (1 H, ddd, J = 15.5, 7.6, 1.5 Hz), 1.48 (9 H, s). 13C NMR (151 MHz, CDCl3): δ = 164.6, 161.8, 142.6, 132.8, 130.1, 129.0, 128.3, 124.7, 119.4, 113.9, 95.7, 85.5, 40.3, 36.6, 27.8. IR (film): 2980, 1744, 1699, 1553, 1468, 1352, 1296, 1283, 1152, 743 cm–1. HRMS (ESI, +): m/z calcd for C21H24O5N2Na+ [M + Na]+: 407.1577; found: 407.1581. HPLC (OX3, hexane–2-PrOH = 10:1, flow rate = 0.5 mL/min, λ = 210 nm): t R (major) = 12.4 min; t R (minor) = 13.5 min.