Synlett 2012; 23(12): 1805-1808
DOI: 10.1055/s-0031-1290404
letter
© Georg Thieme Verlag Stuttgart · New York

‘Evans Auxiliary’ Based P–N Ligands for Pd-Catalyzed Asymmetric Allylic Alkylation Reactions

Yun Li
a  China Novartis Institutes for BioMedical Research Co.,Ltd. , Building 8, Lane 898 Halei Road, 201203, Shanghai, P. R. of China
,
Fang Liang
a  China Novartis Institutes for BioMedical Research Co.,Ltd. , Building 8, Lane 898 Halei Road, 201203, Shanghai, P. R. of China
,
Rui Wu
a  China Novartis Institutes for BioMedical Research Co.,Ltd. , Building 8, Lane 898 Halei Road, 201203, Shanghai, P. R. of China
,
Qian Li
a  China Novartis Institutes for BioMedical Research Co.,Ltd. , Building 8, Lane 898 Halei Road, 201203, Shanghai, P. R. of China
,
Quan-Rui Wang
b  Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, P. R. of China, Fax: +86(21)61606155   Email: lei-1.jiang@novartis.com
,
Yao-Chang Xu
a  China Novartis Institutes for BioMedical Research Co.,Ltd. , Building 8, Lane 898 Halei Road, 201203, Shanghai, P. R. of China
,
Lei Jiang*
a  China Novartis Institutes for BioMedical Research Co.,Ltd. , Building 8, Lane 898 Halei Road, 201203, Shanghai, P. R. of China
› Author Affiliations
Further Information

Publication History

Received: 16 April 2012

Accepted after revision: 06 May 2012

Publication Date:
14 June 2012 (online)


Abstract

A new type of chiral P–N ligands has been prepared which incorporates the Evans auxiliary as chiral ligand. They were found to act as effective ligands in the Pd-catalyzed allylic alkylation reactions. Using these ligands with allylpalladium chloride dimer as catalyst, the coupling of 1,3-diphenyl-3-acetoxyprop-1-ene and dimethyl malonate proceeded smoothly at –10 °C providing the desired product with enantiomeric excess up to 87% and excellent yield.

Supporting Information

 
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  • 12 Typical Procedure for the Preparation of 1a The reaction mixture of 6a (1.75 g, 6.89 mmol) and ZnCl2 (0.188 g, 1.378 mmol) and 4 Å MS (2.0 g) in THF (34.4 mL) was added 7 (2.00 g, 6.90 mmol) and stirred for 12 h at r.t. After that, the reaction mixture was filtered and diluted with CH2Cl2. The organic phase was washed 3 times with H2O and brine and then separeted and dried over Na2SO4. Organic phase was then concentrated and chromatographed on silica gel, eluted with hexane–EtOAc (2:1) which afford 1a (2.358 g, 65% yield) as a yellowish solid; mp 144–145 °C; [α]D 25 +224 (c 0.76, CHCl3). 1H NMR (400 MHz, DMSO-d 6): δ = 8.90 (d, J = 5.0 Hz, 1 H), 8.27 (dd, J = 3.6, 7.4 Hz, 1 H), 7.62 (t, J = 7.5 Hz, 1 H), 7.52 (t, J = 7.4 Hz, 1 H), 7.42 (d, J = 3.3 Hz, 6 H), 7.36–7.16 (m, 11 H), 7.16–7.03 (m, 2 H), 6.93 (dd, J = 4.8, 7.5 Hz, 1 H), 6.40 (d, J = 7.5 Hz, 1 H), 5.50 (t, J = 8.4 Hz, 1 H), 4.81 (t, J = 8.7 Hz, 1 H), 4.16 (t, J = 8.3 Hz, 1 H). 13C NMR (100 MHz, DMSO-d 6): δ = 160.2 (d, J = 22 Hz), 156.7, 148.6, 139.1 (d, J = 5 Hz), 138.8 (d, J = 4 Hz), 138.5, 136.4 (d, J = 5 Hz), 136.3 (d, J = 6 Hz), 134.2 (d, J = 3 Hz), 134.0 (d, J = 3 Hz), 133.6, 132.1, 130.3, 130.0, 129.8, 129.46 (d, J = 1 Hz), 129.4 (d, J = 1 Hz), 129.1, 128.9, 127.9, 126.6, 119.3, 70.5, 62.2. 31P NMR (162 MHz, DMSO-d 6): δ = –14.4 (s). ESI-MS: m/z = 526.2 [M + H+]. ESI-HRMS: m/z calcd for C34H28N2O2P [M + H+]: 527.1888; found: 527.1882. Compound 1b: 54%; mp 125–126 °C. [α]D 25 +174 (c 1.0, CHCl3). 1H NMR (400 MHz, DMSO-d 6): δ = 8.92 (d, J = 5.0 Hz, 1 H), 8.12 (dd, J = 3.6, 6.9 Hz, 1 H), 7.68–7.53 (m, 1 H), 7.49 (t, J = 7.4 Hz, 1 H), 7.42 (d, J = 2.0 Hz, 6 H), 7.37 (dd, J = 3.5, 5.8 Hz, 1 H), 7.33–7.19 (m, 6 H), 6.89 (dd, J = 5.0, 6.8 Hz, 1 H), 6.46 (dd, J = 3.5, 5.8 Hz, 1 H), 4.53–4.30 (m, 2 H), 4.18 (dd, J = 4.6, 7.2 Hz, 1 H), 1.78–1.53 (m, 1 H), 0.79 (d, J = 6.8 Hz, 3 H), 0.74 (d, J = 6.8 Hz, 3 H). 13C NMR (100 MHz, DMSO-d 6): δ = 159.4 (d, J = 22 Hz), 156.3, 148.1, 138.5, 138.3, 138.2, 135.7 (d, J = 9 Hz), 135.6 (d, J = 9 Hz), 133.6 (d, J = 8 Hz), 133.4 (d, J = 8 Hz), 132.9, 131.5, 130.0, 129.3, 129.2, 128.8 (d, J = 7 Hz), 128.1 (d, J = 4 Hz), 126.2, 119.0, 63.5, 61.2, 54.8, 28.6, 17.1, 14.8. 31P NMR (162 MHz, DMSO-d 6): δ = –14.3 (s). ESI-MS: m/z = 493.2 [M + H+]. ESI-HRMS: m/z calcd for C31H30N2O2P [M + H+]: 493.2044; found: 493.2048
  • 13 General Procedure for the Asymmetric Allylic Alkylation To a Schlenk tube containing allyl palladium(II) chloride dimer (2.90 mg, 0.008 mmol), 1b (15.3 mg, 0.032 mmol), and LiOAc (2.62 mg, 0.040 mmol) were evacuated and backfilled with nitrogen for 3 times, after that, THF (2 mL) was added and stirred for 0.5 h at r.t. Then (E)-1,3-diphenylallyl acetate (100 mg, 0.396 mmol) was added, and the mixture was stirred for another 10 min, dimethyl malonate (157 mg, 1.189 mmol) was added to the reaction mixture followed by BSA (242 mg, 1.189 mmol). The resultant mixture was stirred at –10 °C for 10 h. The reaction was diluted with CH2Cl2 and quenched by sat. aq NH4Cl. The organic layer was washed by H2O and brine 3 times, concentrated and purified with silica gel (EtOAc–hexane, 1:10) afforded 10a (121 mg, 99% yield) as a colorless oil. 1H NMR (400 MHz, CDCl3): δ = 7.34–7.20 (m, 10 H), 6.51–6.46 (d, J = 15.6 Hz, 1 H), 6.37–6.29 (dd, J = 8.4, 15.9 Hz, 1 H), 4.30–4.24 (dd, J = 8.7, 10.8 Hz, 1 H), 3.98–3.94 (d, J = 10.8 Hz, 1 H), 3.71–3.70 (d, J = 3.0 Hz, 3 H), 3.52–3.51 (d, 3 H, J = 3.3 Hz, 3 H). The ee value was determined by SFC (Daicel CHIRALCEL AD-H, column size: 0.46 cm I.D. × 25 cm L, liquid CO2/MeOH = 85:15, flow rate: 2.0 mL/min, λ = 254 nm): t R (major) = 8.0 min; t R (minor) = 16.77 min; 87% ee