Synthesis of Functionalized Allylsilanes via the Condensation of α,β-Unsaturated Carbonyl Compounds with γ-Trimethylsilylmethylallylzircocene Followed by Anionic Oxy-Cope Rearrangement

Jin-Hong Pi; Xian Huang

doi:10.1055/s-2003-42126

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Synlett 2003(15): 2413-2415
DOI: 10.1055/s-2003-42126

LETTER

Synthesis of Functionalized Allylsilanes via the Condensation of α,β-Unsaturated Carbonyl Compounds with γ-Trimethylsilylmethylallylzircocene Followed by Anionic Oxy-Cope Rearrangement

Jin-Hong Pi^a, Xian Huang*^a,b
^a Department of Chemistry, Zhejiang University, Xi-xi Campus, Hangzhou, 310028, P. R. China
^b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, P. R. China
e-Mail: huangx@mail.hz.zj.cn;

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Publication History

Received 17 September 2003
Publication Date:
07 November 2003 (online)

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Abstract

Condensation of α,β-unsaturated carbonyl compounds with γ-trimethylsilylmethylallylzircocene followed by anionic oxy-Cope rearrangement provided a novel method for the synthesis of functionalized allylsilanes compounds possessing a carbonyl group in the same molecule, which are versatile intermediates for intramolecular allylsilylation, giving cyclopentanols on treatment with n-Bu₄NF.

Key words

allylzirconcene - oxy-Cope rearrangement - allylsiliane - cyclopentanol

References

1 Hill RK. In Comprehensive Organic Synthesis Trost BM. Fleming I. Pergamon; Oxford: 1991. Chap. 7.1.

Google Scholar
2 Wilson SR. Org. React. 1993, 43: 93

Google Scholar
3 Paquette LA. Synlett 1990, 67

Article in Thieme Connect Google Scholar
4 Paquette LA. Angew. Chem., Int. Ed. Engl. 1990, 29: 609

Google Scholar
5 Paquette LA. Chem. Soc. Rev. 1995, 9

Crossref Google Scholar
6 Wipf P. Jahn H. Tetrahedron 1996, 52: 12853

Google Scholar
7a Maeta H. Hasegawa T. Suzuki K. Synlett 1993, 341

Google Scholar
7b Chino M. Matsumoto T. Suzuki K. Synlett 1994, 359

Google Scholar
7c Suzuki S. Hasegawa T. Imai T. Maeta H. Ohba S. Tetrahedron 1995, 51: 4483

Google Scholar
7d Chio M. Lianf GH. Matsumoto T. Suzuki K. Chem. Lett. 1996, 231

Google Scholar
9 Macdonald TL. Natalie KJ. Prasad G. Sawyer JS. J. Org. Chem. 1986, 51: 1124

Crossref Google Scholar
11 Paquette LA. Tetrahedron 1997, 53: 13971

Crossref Google Scholar

8

General Procedure for Preparation of 4-Trimethyl-silylmethyl-1,5-dien-3-ols: Under a N₂ atmosphere at -78 °C, to a stirred suspension of Cp₂Zr(H)Cl (2 mmol) in CH₂Cl₂(5 mL) was added allene 1 (3 mmol) in CH₂Cl₂ (3 mL). The reaction was gradually warmed up to r.t., resulting in a red solution. The reaction was re-chilled to -78 °C (or 0 °C), to which a solution of aldehyde (or ketone) (1 mmol) in CH₂Cl₂(5 mL) was added. After 30 min, the reaction was quenched by adding sat. aq NaHCO₃. Extractive workup followed by purification (SiO₂ preparative TLC, hexane) gave 4 and 5. Selected Data of 4e: IR(neat): 1930, 11875, 1600, 1490, 1450, 1410, 1375, 1325, 1175, 1060, 853 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 6.54 (d, J = 8.0Hz, 1 H), 6.34 (d, J = 8.0 Hz, 1 H), 5.56 (ddd, J = 16.4, 10.8, 9.6 Hz, 1 H), 5.19 (d, J = 10.8 Hz, 1 H), 5.17 (d, J = 16.4 Hz, 1 H), 2.28(m, 1 H), 2.2.02 (br s, 2 H), 1.54 (m, 1 H), 1.35 (s, 3 H), 0.98 (m, 1 H), 0.63 (m, 1 H), 0.08 (s, 9 H). ¹³C NMR (100 MHz, CDCl₃): δ = 140.7, 136.5, 136.2, 132.0, 128.4, 127.4, 121.4 118.6, 75.4 52.3, 26.3, 17.4, 0.35. MS (EI): m/z (%) = 354 (2.86), 105(100). Anal. Calcd for C₁₇H₂₅BrOSi: C, 57.78; H, 7.13. Found: C, 58.04; H, 7.26.

10

General Procedure for Preparation of 7:
KH (30% dispersion in mineral oil, 5 mmol) was washed with anhyd hexanes and suspended in THF (8 mL) to which I₂ (0.15 mmol) and 4-trimethylsilylmethyl-1,5-dien-3-ol (1 mmol) were added and the mixture was stirred at r.t. for 7 h. Upon cooling to 0 °C, the reaction mixture was quenched by adding 10% aq NH₄Cl solution and the aq layer extracted with Et₂O (3 × 10 mL). The combined organic layers were washed with sat. NaCl, dried over anhyd MgSO₄, filtered and concentrated. Purification by flash chromatography (hexane-EtOAc = 15:1) gave allylsilane.
Selected Data of 7c: IR(neat): 1690, 1665, 1611, 1590, 1565, 1485, 860, 750, 695 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.08-7.12 (m, 4 H), 5.38 (dt, J = 16.0, 8.0 Hz, 1 H), 5.10 (dt, J = 16.0, 6.4 Hz, 1 H), 3.16 (m, 1 H), 2.72 (m, 2 H), 2.32 (s, 3 H), 2.28 (m, 2 H), 2.02 (s, 3 H), 1.37 (d, J = 8.0 Hz, 2 H), -0.06 (s, 9 H). ¹³C NMR (100 MHz, CDCl₃): δ = 207.7, 144.5, 131.0, 128.9, 127.8, 127.6, 126.9, 51.3, 41.4, 31.8, 24.9, 21.4, -1.59. MS (EI): m/z (%) = 289 (2.12), 73(100). Anal. Calcd for C₁₈H₂₈OSi: C, 74.94; H, 9.78. Found: C, 75.11; H, 10.04.

12

General Procedure for Preparation of 10:
To a solution of allylsilane (1mmol) in THF (8 mL) was added n-Bu₄NF (2 mmol) and the mixture was stirred at r.t. for 2 h. The reaction mixture was quenched with 10% aq NH₄Cl solution and the aq layer was extracted with Et₂O (3 × 10 mL). The combined organic layers were washed with water and sat. NaCl, dried over anhyd MgSO₄, filtered and concentrated. Purification by flash chromatography (hexane-EtOAc = 10:1) gave 10. Selected Data of 10b: ¹H NMR (400 MHz, CDCl₃): δ = 7.20-7.38 (m, 5 H), 5.87 (ddd, J = 8.4, 10.0, 17.2 Hz, 1 H), 5.14 (d, J = 17.2 Hz, 1 H), 5.12 (d, J = 10.0 Hz, 1 H), 348 (m, 1 H), 2.72 (m, 1 H), 2.31 (m, 1 H), 2.08 (br s, 1 H), 1.88 (m, 1 H), 1.70 (m, 1 H), 1.33 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 145.4, 139.2, 128.8, 127.4, 126.5, 115.9, 81.3, 56.9, 49.7, 42.3, 40.1, 26.8. MS (EI): m/z (%) = 202(5.7). Anal. Calcd for C₁₄H₁₈O: C, 83.12; H, 8.97. Found: C, 83.43; H, 9.06.