Mild and Efficient Allylation of Aldehydes with Allyltributylstannane Promoted by MgI₂·(OEt)_n Etherate

Abstract

Allylation of aldehydes with allyltributylstannane was promoted in the presence of MgI₂·(OEt)_n to give homoallylic alcohols. The iodide anion and a noncoordinating reaction medium (CH₂Cl₂) are the key features of this catalytic system.

magnesium iodide - allylation - aldehyde - allyltributylstannane

References and Notes

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Typical Procedure for the Synthesis of Homoallylic Alcohols: To a stirred solution of benzaldehyde (0.5 mmol) in CH₂Cl₂ (3 mL) was added a freshly prepared solution of MgI₂·(OEt)_n in Et₂O-benzene (1:2, 1.0 M, 0.5 mL) at r.t. After stirring for 10 min, a solution of allyltributylstannane (0.6 mmol) in CH₂Cl₂ (2 mL) was added dropwise via a syringe. The resulting homogeneous reaction mixture was stirred at r.t. for 3 h and quenched with distillated H₂O. Extractive workup with Et₂O and chromatographic purification of the crude product on silica gel gave the homoallylic alcohol 1a in 92% yield.

19

Selected spectroscopic data:
Compound 1a:^{20 1}H NMR (400 MHz, CDCl₃): δ = 2.13 (br s, 1 H), 2.47-2.52 (m, 2 H), 4.72 (t, J = 6.5 Hz, 1 H), 5.11-5.19 (m, 2 H), 5.76-5.85 (m, 1 H), 7.25-7.29 (m, 1 H), 7.32-7.35 (m, 4 H). Compound 1b:^{10 1}H NMR (400 MHz, CDCl₃): δ = 2.15 (br s, 1 H), 2.43-2.52 (m, 1 H), 2.54-2.62 (m, 1 H), 4.85-4.89 (m, 1 H), 5.18-5.22 (m, 2 H), 5.75-5.84 (m, 1 H), 7.53 (t, J = 8.0 Hz, 1 H), 7.70 (d, J = 7.6 Hz, 1 H), 8.14 (d, J = 8.1 Hz, 1 H), 8.25 (s, 1 H). Compound 1c:^{10 1}H NMR (400 MHz, CDCl₃): δ = 2.48-2.63 (m, 2 H), 2.82 (br s, 1 H), 4.90 (t, J = 6.2 Hz, 1 H), 5.17-5.22 (m, 2 H), 5.77-5.87 (m, 1 H), 7.56 (d, J = 8.0 Hz, 2 H), 8.21 (d, J = 8.0 Hz, 2 H). Compound 1d:^{21 1}H NMR (400 MHz, CDCl₃): δ = 2.45-2.49 (m, 2 H), 3.77 (s, 3 H), 4.65 (t, J = 6.5 Hz, 1 H), 5.08-5.16 (m, 2 H), 5.72-5.82 (m, 1 H), 6.78 (d, J = 8.2 Hz, 1 H), 6.88-6.91 (m, 2 H), 7.23 (t, J = 8.0 Hz, 1 H). Compound 1e:^{22 1}H NMR (400 MHz, CDCl₃): δ = 2.32-2.41 (m, 2 H), 2.58-2.63 (m, 1 H), 5.12-5.20 (m, 3 H), 5.79-5.90 (m, 1 H), 7.16-7.33 (m, 3 H), 7.54 (d, J = 7.6 Hz, 1 H). Compound 1f:^{9 1}H NMR (400 MHz, CDCl₃): δ = 2.31 (d, J = 2.9 Hz, 1 H), 2.41-2.49 (m, 2 H), 4.67-4.69 (m, 1 H), 5.12-5.16 (m, 2 H), 5.72-5.79 (m, 1 H), 7.25-7.31 (m, 4 H). Compound 1g:^{10 1}H NMR (400 MHz, CDCl₃): δ = 2.21 (br s, 1 H), 2.33 (s, 3 H), 2.45-2.50 (m, 2 H), 4.66 (t, J = 6.5 Hz, 1 H), 5.08-5.16 (m, 2 H), 5.74-5.82 (m, 1 H), 7.14 (d, J = 7.7 Hz, 2 H), 7.22 (d, J = 7.5 Hz, 2 H). Compound 1h:^{20 1}H NMR (400 MHz, CDCl₃): δ = 2.09 (br s, 1 H), 2.35-2.44 (m, 2 H), 4.34 (br s, 1 H), 5.14-5.19 (m, 2 H), 5.79-5.90 (m, 1 H), 6.23 (dd, J = 7.9, 15.9 Hz, 1 H), 6.59 (d, J = 15.9 Hz, 1 H), 7.21-7.37 (m, 5 H). Compound 1i:^{23 1}H NMR (400 MHz, CDCl₃): δ = 1.66 (br s, 1 H), 1.70 (d, J = 6.5 Hz, 3 H), 2.24-2.35 (m, 2 H), 4.08-4.15 (m, 1 H), 5.11-5.17 (m, 2 H), 5.51 (dd, J = 6.8, 15.2 Hz, 1 H), 5.65-5.73 (m, 1 H), 5.75-5.85 (m, 1 H). Compound 1j:^{10 1}H NMR (400 MHz, CDCl₃): δ = 1.73-1.81 (m, 2 H), 1.89 (br s, 1 H), 2.14-2.21 (m, 1 H), 2.26-2.32 (m, 1 H), 2.64-2.71 (m, 1 H), 2.75-2.83 (m, 1 H), 3.64-3.70 (m, 1 H), 5.10-5.15 (m, 2 H), 5.74-5.85 (m, 1 H), 7.15-7.30 (m, 5 H). Compound 1k:^{24 1}H NMR (400 MHz, CDCl₃): δ = 0.86 (t, J = 7.0 Hz, 3 H), 1.21-1.50 (m, 12 H), 1.65 (br s, 1 H), 2.05-2.21 (m, 1 H), 2.27-2.38 (m, 1 H), 3.58-3.72 (m, 1 H), 5.12-5.19 (m, 2 H), 5.77-5.95 (m, 1 H). Compound 1l:^{22 1}H NMR (400 MHz, CDCl₃): δ = 0.90 (t, J = 7.0 Hz, 3 H), 1.24-1.48 (m, 6 H), 1.72 (br s, 1 H), 2.12-2.16 (m, 1 H), 2.15-2.33 (m, 1 H), 3.60-3.65 (m, 1 H), 5.10-5.17 (m, 2 H), 5.77-5.90 (m, 1 H). Compound 1m:²⁵ [α]²⁴ _D -21.2 (c = 1.02, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 1.35 (s, 9 H), 2.20-2.30 (m, 2 H), 2.83-2.94 (m, 2 H), 3.59 (td, J = 1.5, 7.0 Hz, 1 H), 3.73 (br q, J = 8.0 Hz, 1 H), 4.88 (d, J = 9.5 Hz, 1 H), 5.10-5.15 (m, 2 H), 5.70-5.80 (m, 1 H), 7.18-7.32 (m, 5 H). Compound 1n:²⁶ [α]²⁴ _D +15.1 (c = 1.0, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 1.36 (s, 3 H), 1.43 (s, 3 H), 2.16-2.24 (m, 1 H), 2.25-2.37 (m, 1 H), 2.41 (br s, 1 H, OH), 3.62-3.78 (m, 1 H), 3.90-3.95 (m, 1 H), 3.98-4.06 (m, 2 H), 5.10-5.17 (m, 2 H), 5.80-5.91 (m, 1 H).

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