Regiocontrolled Addition of Carbonyl Compounds with Allylic Indium Generated by Hydroindation of 1,3-Dienes

Naoki Hayashi; Hiroyuki Honda; Ikuya Shibata; Makoto Yasuda; Akio Baba

doi:10.1055/s-2008-1072753

LETTER

Regiocontrolled Addition of Carbonyl Compounds with Allylic Indium Generated by Hydroindation of 1,3-Dienes

Naoki Hayashi^a, Hiroyuki Honda^a, Ikuya Shibata*^b, Makoto Yasuda^a, Akio Baba*^a
^a Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
^b Research Center for Environmental Preservation, Osaka University, 2-4 Yamadaoka, Suita, Osaka 565-0871, Japan
Fax: +81(6)68798978; e-Mail: shibata@epc.osaka-u.ac.jp;

Abstract

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Abstract

Allylic indiums, generated by a conjugate hydroindation of 1,3-dienes by HInCl₂, reacted with carbonyl compounds in a one-pot treatment. Both γ- and α-adducts can be obtained depending upon the conditions used.

Key words

allylation - hydrides - indium - ketones - regioselectivity

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References

References and Notes

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Typical Procedure A 10 mL round-bottom flask charged with InCl₃ (2.0 mmol) was dried by heating to 110 °C under reduced pressure (1 mmHg) for 1 h. After the nitrogen was filled, THF (2 mL) was added to dissolve InCl₃. To the mixture was added Bu₃SnH (2.0 mmol) at -78 °C. The mixture was then stirred for 10 min to prepare dichloroindium hydride (HInCl₂). After the solution was warmed up to r.t., 2,3-dimethyl-1,3-butadiene (1a, 4.0 mmol) was added and the resulting mixture was stirred for 5 h. Then benzil (2b, 1.0 mmol) was added and stirred for 14 h. The resulting mixture was quenched by aq 1 N HCl (5 mL) and extracted with Et₂O
(3 × 10 mL). The combined organic layer was treated with aq NH₄F and then the precipitate was filtered to remove the tin compound. The filtrate was extracted with Et₂O and dried over MgSO₄. Concentration followed by silica gel column chromatography eluting with hexane-EtOAc (90:10) afforded 4ab as a solid.

Analytical and Spectroscopic Data of Selected Compounds Compound 3ab: mp 65-66 °C. IR (KBr): 3494 (OH), 1685 (C=O) cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.67-7.59 (m, 4 H), 7.37-7.23 (m, 6 H), 5.12 (s, 1 H), 5.02 (s, 1 H), 3.52 (s, 1 H), 1.56 (s, 3 H), 1.46 (s, 3 H), 1.23 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 203.43, 151.81, 138.62, 138.42, 131.38, 129.46, 127.79, 127.62, 127.56, 127.15, 115.61, 83.54, 49.37, 24.49, 24.15, 22.85. MS (CI): m/z = 295 (70) [M⁺ + 1], 278 (22), 277 (100), 212 (20), 211 (86), 105(34). HRMS (CI, +0.9 mmu): m/z calcd for C₂₀H₂₃O₂: 295.1698; found: 295.1707 [M⁺ + 1].
Compound 4ab: mp 88-89 °C. IR (KBr): 3498 (OH), 1670 (C=O) cm^-1; ¹H NMR (400 MHz, CDCl₃): δ = 7.89-7.79 (m, 2 H), 7.63-7.53 (m, 2 H), 7.43-7.25 (m, 6 H), 3.63 (s, 1 H), 3.40 (d, J = 13.8 Hz, 1 H), 2.96 (d, J = 13.8 Hz, 1 H), 1.66 (s, 3 H), 1.61 (s, 3 H), 1.39 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 201.39, 143.14, 135.29, 132.61, 132.35, 130.32, 128.69, 127.89, 127.54, 125.11, 122.84, 81.80, 44.66, 21.22, 21.02, 19.74. MS (CI): m/z = 295 (67) [M⁺ + 1], 278 (22), 277 (100). HRMS (CI, +0.5 mmu): m/z calcd for C₂₀H₂₃O₂: 295.1698; found: 295.1703 [M⁺ + 1].
Compound 4ac: IR (neat): 3514 (OH), 1732 (C=O) cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.65 (d, J = 8.0 Hz, 2 H), 7.35 (dd, J = 8.0, 7.5 Hz, 2 H), 7.29 (d, J = 7.5 Hz, 1 H), 3.74 (s, 3 H), 3.50 (s, 1 H), 3.10 (d, J = 13.8 Hz, 1 H), 2.87 (d, J = 13.8 Hz, 1 H), 1.68 (s, 6 H), 1.60 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 175.59, 142.20, 131.19, 128.08, 127.58, 125.64, 122.15, 78.00, 52.91, 44.71, 21.11, 21.00, 19.48. MS (EI, 70 eV): m/z = 248 (1) [M⁺], 105 (100), 84 (39), 77 (23). HRMS (EI, +0.2 mmu): m/z calcd for C₁₅H₂₀O₃: 248.1412; found: 248.1414 [M⁺].
Compound 4ad: IR (neat): 3564 (OH) cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.44 (d, J = 8.0 Hz, 2 H), 7.31 (dd, J = 8.0, 7.2 Hz, 2 H), 7.23 (t, J = 7.2 Hz, 1 H), 3.67 (d, J = 9.3 Hz, 1 H), 3.57 (d, J = 9.3 Hz, 1 H), 3.37 (s, 3 H), 2.78 (s, 1 H), 2.75 (d, J = 13.8 Hz, 1 H), 2.47 (d, J = 13.8 Hz, 1 H), 1.61 (s, 3 H), 1.53 (s, 3 H), 1.41 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 145.12, 129.66, 127.85, 126.61, 125.33, 123.35, 79.10, 76.51, 59.35, 44.15, 20.92, 20.78, 20.41. MS (CI): m/z = 235 (1) [M⁺ + 1], 217 (100), 151 (32). HRMS (CI, -0.2 mmu): m/z calcd for C₁₅H₂₃O₂: 235.1698; found: 235.1696 [M⁺ + 1].

Although we tried the reaction of simple acetophenone (2e) with diene 1a in the presence of equimolar amount of Lewis basic additives such as Ph₃P and HMPA, only a small amount of α-adduct 4ae was obtained at r.t. So we think that intramolecular coordination is more important than intermolecular coordination by ligand.