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Synlett 2015; 26(11): 1510-1514
DOI: 10.1055/s-0034-1378709
letter
© Georg Thieme Verlag Stuttgart · New York

Kinetic Resolution of Unsymmetrical Acyclic Allyl Carbonates Using Trimethylsilyl Cyanide via Palladium-Catalyzed Asymmetric Allylic Alkylation

Da-Chang Bai
a   State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling Ling Road, Shanghai 200032, P. R. of China
,
Wan-Ying Wang
a   State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling Ling Road, Shanghai 200032, P. R. of China
,
Chang-Hua Ding
a   State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling Ling Road, Shanghai 200032, P. R. of China
,
Xue-Long Hou*
a   State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling Ling Road, Shanghai 200032, P. R. of China
› Author Affiliations
Further Information

Publication History

Received: 09 March 2015

Accepted after revision: 07 May 2015

Publication Date:
01 June 2015 (online)

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This paper is dedicated to Professor K. P. C. Vollhardt

Abstract

The kinetic resolution of 1,3-disubstituted unsymmetrical ­allylic substrates with TMSCN as the nucleophile was realized via palladium-catalyzed asymmetric allylic alkylation, providing optically active allylic substrates and β,γ-unsaturated nitriles in good yield and enantioselectivity.

Key words

kinetic resolution - palladium - asymmetric allylic alkylation - unsymmetrical acylic allyl carbonates - trimethylsilyl cyanide

Supporting Information

    Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1378709.
  • Supporting Information
 

  • References and Notes

  • 1 These authors contributed equally.
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  • 10 General Procedure for Kinetic Resolution [Pd(η3-C3H5)Cl]2 (2.0 mg, 0.006 mmol) and ligand (R,R)-L (8.0 mg, 0.006 mmol) and toluene (1.0 mL) were added into a dry sealed tube (10 mL) and stirred at r.t. for 30 min. Compound 1 (0.2 mmol), TMSCN (30 μL, 0.2 mmol), and toluene (1.0 mL) were added to the sealed tube, then the reaction mixture was stirred at 120 °C immediately. After the reaction time show in Table 2, the reaction mixture was quenched by sat. Na2CO3 (0.5 mL) and extracted with EtOAc (3 × 10 mL). The organic layer was combined, dried (anhydrous Na2SO4), filtered, and concentrated in vacuo to afford a crude oil. Purification by chromatography on silica gel provided the desired product (eluting with PE–EtOAc = 10:1) Compound 2c: Yield 45%; 59% ee. [α]D 20 = 8.8 (c 0.44, CHCl3).4 1H NMR (400 MHz CDCl3): δ = 7.26–7.39 (m, 5 H), 6.70–6.74 (d, J = 16.0 Hz, 1 H), 6.04–6.10 (dd, J = 16.0, 7.2 Hz, 1 H), 3.50 (m, 1 H), 1.50 (d,J = 7.2 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 135.7, 132.5, 128.7, 128.3, 126.5, 124.3, 120.9, 28.4, 19.1. MS (EI): m/z (rel. intensity) = 157 (66) [M+], 158 (7), 156 (79), 142 (38), 129 (30), 115 (100), 102 (10), 91 (11), 89 (12), 77 (20), 63 (14), 51 (22). IR (film): ν = 2985 (w), 2242 (w), 1496 (w), 1449 (m), 1399 (m), 964 (m), 745 (s), 692 (s) cm–1. HPLC (Chiralcel OD-H, hexane–2-PrOH = 95:5, 0.7 mL/min, 214 nm): t R (major) = 12.14 min; t R (minor) = 13.46 min. HRMS: m/z calcd for C11H10N [M+]: 157.0891; found: 157.0889. Compound 1c: Yield 51%; 88% ee. [α]D 20 = –75.8 (c 0.8, CHCl3). 1H NMR (400 MHz CDCl3): δ = 7.24–7.40 (m, 4 H), 6.63–6.67 (d, J = 16.0 Hz, 1 H), 6.18–6.24 (dd, J = 16.0, 7.2 Hz, 1 H), 5.36 (m, 1 H), 3.92 (d,J = 6.8 Hz, 2 H), 1.97 (m, 1 H), 1.46 (d,J = 5.6 Hz, 3 H), 0.95 (d, J = 7.2 Hz, 6 H). MS (EI): m/z (rel. intensity) = 248 (8.0) [M+], 205 (7), 192 (1), 148 (39), 131 (100), 115 (43), 105 (31), 91 (59), 77 (16), 57 (46), 51 (8). HPLC (Chiralcel OD-H, hexane–2-PrOH = 99:1, 0.7 mL/min, 214 nm): t R (major) = 7.18 min; t R (minor) = 7.80 min. Compound 2i: Yield 42%; 60% ee. [α]D 20 = 8.4 (c 0.8, CHCl3). 1HNMR (400 MHz,CDCl3): δ = 7.21–7.26 (m, 1 H), 6.97 (d, J = 7.6 Hz, 1 H), 6.90 (s, 1 H), 6.83 (dd, J = 8.4, 2.4 Hz, 1 H), 6.66–6.70 (d, J = 15.6 Hz, 1 H), 6.06 (dd, J = 16.0, 6.4 Hz, 1 H), 3.82 (m, 1 H), 3.51 (m, 1 H), 1.5 (d, J = 7.2 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 159.8, 137.1, 132.4, 129.7, 124.6, 120.9, 119.1, 113.9, 111.9, 55.3, 28.4, 19.0. MS (EI): m/z (rel. intensity): 187 (100) [M+], 186 (57), 172 (23), 156 (22), 144 (94), 128 (20), 115 (48), 102 (24), 91 (22), 77 (22), 63 (23), 51 (18). IR (film): ν = 2938 (m), 2836 (m), 2241 (m), 1599 (s), 1579 (s), 1453 (m), 1263 (m), 1041 (m), 964 (s), 775 (s), 688 (s) cm–1. HPLC (Chiralpak PA-2, hexane–2-PrOH = 99:1, 1.0 mL/min, 214 nm): t R (major) = 27.98 min; t R (minor) = 31.74 min. HRMS: m/z calcd for C12H13NO [M+]: 187.0994; found: 187.0997. Compound 1i: Yield 48%; 74% ee. [α]D 20 = –60.4 (c 1.3, CHCl3). 1H NMR (400 MHz,CDCl3): δ = 7.21–7.26 (m, 1 H), 6.97 (d, J = 7.6 Hz, 1 H), 6.90 (s, 1 H), 6.83 (dd, J = 8.0, 2.0 Hz, 1 H), 6.66–6.70 (d, J = 16.0 Hz, 1 H), 6.06 (dd, J = 16.0, 6.4 Hz, 1 H), 5.36 (m, 1 H), 3.92 (d, J = 6.8 Hz, 1 H), 3.91 (s, 3 H), 1.97 (m, 1 H), 1.46 (d,J = 6.4 Hz, 2 H), 0.92 (d, J = 6.4 Hz, 9 H). MS (EI): m/z (rel. intensity): 278 (32) [M+], 235 (2), 178 (33), 161 (75), 145 (42), 135 (100), 129 (18), 117 (26), 91 (34), 77 (14), 57 (51). HPLC (Chiralpak OJ-H, hexane–2-PrOH = 99.5:0.5, 0.7 mL/min, 214 nm): t R (major) = 23.67 min; t R (minor) = 29.92. Compound 2p: Yield 39%; 43% ee. [α]D 20 = 2.4 (c 0.85, CHCl3). 1H NMR (400 MHz,CDCl3): δ = 7.25–7.40 (m, 5 H), 6.81–6.72 (d, J = 16.0 Hz, 1 H), 6.01 (dd, J = 16.0, 6.8 Hz, 1 H), 3.36 (m, 1 H), 1.67–1.82 (m, 6 H), 1.19–1.26 (m, 5 H). 13C NMR (101 MHz, CDCl3): δ = 135.8, 133.9, 128.7, 128.1, 126.5, 122.1, 119.4, 41.1, 40.8, 31.0, 29.6, 26.0, 25.8. MS (EI): m/z (rel. intensity): 225 (8) [M+], 143 (100), 128 (2), 115 (25), 102 (2), 91 (4), 83 (13), 65 (3), 55 (46). IR (film): ν = 2922 (m), 2854 (m), 2233 (w), 1449 (m), 974 (m), 746 (s), 691 (m) cm–1. HPLC (Chiralpak AD-H, hexane–2-PrOH = 99:1, 0.7 mL/min, 214 nm): t R (minor) = 20.65 min; t R (major) = 30.04 min. HRMS: m/z calcd for C16H19N [M+]: 225.1514; found: 225.1517. Compound 1p: Yield 34%; 97% ee. [α]D 20 = –29.5 (c 1.0, CHCl3). 1H NMR (400 MHz, CDCl3): δ = 7.25–7.40 (m, 5 H), 6.65 (d, J = 16.0 Hz, 1 H), 6.15 (dd, J = 16.0, 8.0 Hz, 1 H), 5.03 (m, 1 H), 3.92 (d, J = 6.8 Hz, 1 H), 2.02 (m, 1 H), 1.88 (m, 1 H), 1.60–1.82 (m, 5 H), 1.01–1.20 (m, 5 H), 0.92 (dd, J = 6.8, 2.0 Hz, 6 H). MS (EI): m/z (rel. intensity): 316 (3) [M+], 216 (12), 199 (14), 169 (3), 156 (6), 141 (11), 133 (100), 117 (35), 91 (25), 83 (16), 57 (41), 55 (32). HPLC (Chiralpak OD-H, hexane–2-PrOH = 99.5:0.5, 0.7 mL/min, 214 nm): t R (minor) = 20.65 min; t R (major) = 30.04 min.
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