Phosphomolybdic Acid-Catalyzed Efficient Three-Component Reaction: A Facile Synthesis of Protected Homoallylic Amines

G. Smitha; Bruhaspathy Miriyala; John S. Williamson

doi:10.1055/s-2005-863723

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Synlett 2005(5): 0839-0841
DOI: 10.1055/s-2005-863723

LETTER

Phosphomolybdic Acid-Catalyzed Efficient Three-Component Reaction: A Facile Synthesis of Protected Homoallylic Amines

G. Smitha, Bruhaspathy Miriyala, John S. Williamson*
Department of Medicinal Chemistry, School of Pharmacy, University of Mississippi, MS 38677, USA
Fax: +1(662)9155638; e-Mail: mcjsw@olemiss.edu;

Further Information

Publication History

Received 10 December 2004
Publication Date:
09 March 2005 (online)

Abstract
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Abstract

A new and efficient phosphomolybdic acid (H₃PMo₁₂O₄₀)-catalyzed three-component reaction of aldehydes, carbamate and allyltrimethylsilane to yield the corresponding protected homoallylic amines in good yields is described.

Key words

phosphomolybdic acid - three-component reaction - homoallylic amines - heteropolyacid

References

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11

Spectroscopic data for the selected products:
Table 1, Entry 3: ¹H NMR (400 MHz, CDCl₃): δ = 7.65 (d, J = 7.6 Hz, 2 H), 7.45 (t, J = 7.6 Hz, 1 H), 7.34 (t, J = 7.6 Hz, 2 H), 7.18-7.14 (m, 3 H), 7.07-7.04 (m, 2 H), 5.55-5.47 (m, 1 H), 5.08-5.04 (m, 2 H), 4.93 (br s, 1 H), 4.42-4.40 (m, 1 H), 2.46 (t, J = 5.2 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 140.6, 140.3, 133.2, 132.2, 128.7 (2 C), 128.3 (2 C), 127.4, 127.0 (2 C), 126.6 (2 C), 118.9, 57.6, 41.8. IR (neat): 3276, 2949, 2331, 1319, 1161, 753 cm^-1. HRMS (ESI): m/z calcd for C₁₆H₁₇NO₂S: 310.0877 [M + Na]⁺; found: 310.0870.
Table 2, Entry 8: ¹H NMR (500 MHz, CDCl₃): δ = 7.35-7.26 (m, 5 H), 7.18 (d, J = 7.5 Hz, 2 H), 6.85 (d, J = 8.5 Hz, 2 H), 5.67-5.61 (m, 1 H), 5.30-5.10 (m, 5 H), 4.85 (br s, 1 H), 2.56 (br s, 1 H), 1.05 (s, 9 H), 0.26 (s, 6 H). ¹³C NMR (125 MHz, CDCl₃): δ = 155.6, 154.6, 136.5, 134.7, 133.9, 128.4 (2 C), 128.0 (2 C), 127.3 (2 C), 119.9 (3 C), 118.1, 66.9, 54.5, 41.3, 26.1 (3 C), 18.6, -3.8 (2 C). IR (neat): 3325, 2929, 1698, 1509, 1256, 914 cm^-1. HRMS (ESI): m/z calcd for C₂₄H₃₃NO₃Si: 434.2127 [M + Na]⁺; found: 434.2120.
Table 2, Entry 9: ¹H NMR (500 MHz, CDCl₃): δ = 7.41-7.34 (m, 5 H), 7.24 (dd, J = 2.0, 6.0 Hz, 2 H), 7.16 (d, J = 8.0 Hz, 1 H), 7.01 (t, J = 7.5 Hz, 1 H), 5.80-5.70 (m, 2 H), 5.30 (s, 2 H), 5.17-5.08 (m, 5 H), 3.52 (s, 3 H), 2.64 (t, J = 6.0 Hz, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 155.5, 154.2, 136.6, 134.5, 130.2, 128.4, 128.3, 128.1, 128.0, 127.9, 121.7 (3 C), 117.7, 114.2, 94.3, 66.8, 56.4, 52.2, 40.3. IR (neat): 3342, 2954, 1716, 1492, 1233, 995 cm^-1. HRMS (ESI): m/z calcd for C₂₀H₂₃NO₄: 364.1524 [M + Na]⁺; found: 364.1517.
Table 2, Entry 12: ¹H NMR (400 MHz, CDCl₃): δ = 7.92 (d, J = 8.0 Hz, 2 H,), 7.43-7.34 (m, 7 H), 5.66-5.58 (m, 1 H), 5.14-5.02 (m, 4 H), 4.85 (br s, 1 H), 2.58 (s, 5 H). ¹³C NMR (100 MHz, CDCl₃): δ = 197.8, 155.9, 136.2, 133.4, 128.7 (3 C), 128.5 (2 C), 128.1 (2 C), 128.0 (2 C), 126.5 (2 C), 118.7, 116.5, 66.8, 40.8, 26.5. IR (neat): 3329, 3065, 1708, 1681, 1530, 1219, 698 cm^-1. HRMS (ESI): m/z calcd for C₂₀H₂₁NO₃: 346.1417 [M + Na]⁺; found: 346.1409.