A Concise Synthesis of (+)-Goniodiol Using a Catalytic Hetero Diels-Alder/Allylboration Sequence

Abstract

A new short and efficient synthesis of (+)-goniodiol is reported using a catalytic asymmetric hetero Diels-Alder/allylboration sequence.

Key words

asymmetric catalysis - hetero Diels-Alder - allylboration reaction - (+)-goniodiol

References

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14

The absolute configuration of the four stereocenters was confirmed by the examination of its X-ray crystal structure. See ref. 11b.

15

At this temperature, we observed a slow transformation of aldehyde 4 into benzaldehyde.

16

The stereoselectivity of 7 has been studied with various chiral aldehydes. These results will be reported elsewhere.

20

All new compounds were fully characterized (¹H NMR, ¹³C NMR, elemental analysis or HRMS).
Compound 9: [α]_D ²⁰ -145.9 (c 1.11, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 1.20 (t, 3 H, J = 7.1 Hz), 2.12 (m, 2 H), 3.33 (dq, 1 H, J = 7.1, 9.5 Hz), 3.80 (dq, 1 H, J = 7.1, 9.0 Hz), 4.09 (m, 1 H), 4.40 (dd, 1 H, J = 3.6, 7.4 Hz), 4.92 (dd, 1 H, J = 3.8, 7.8 Hz), 5.34 (m, 1 H), 5.79 (m, 1 H), 5.82 (d, 1 H, J = 7.8 Hz), 7.32 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 15.2, 30.5, 64.2, 71.8, 79.7, 80.8, 98.0, 123.5, 127.2, 126.3, 128.5, 129.1, 132.9, 154.5. Anal. Calcd for C₁₆H₁₈O₅: C, 66.20; H, 6.25. Found: C, 66.22; H, 6.33.
Compound 11: [α]_D ²⁰ -144.3 (c 0.62, CH₂Cl₂). ¹H NMR (300 MHz, CDCl₃): δ = 2.22 (m, 1 H), 2.70 (m, 1 H), 4.15 (ddd, 1 H, J = 1.1, 3.8, 12.8 Hz), 4.98 (dd, 1 H, J = 1.1, 8.1 Hz), 5.87 (dd, 1 H, J = 2.3, 9.9 Hz), 5.98 (d, 1 H, J = 8.1 Hz), 6.85 (ddd, 1 H, J = 2.1, 6.4, 9.9 Hz), 7.48 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 29.6, 72.8, 78.0, 79.2, 119.7, 123.7, 125.3, 127.7, 128.4, 130.4, 153.0, 160.8. Anal. Calcd for C₁₄H₁₂O₅: C, 64.61; H, 4.65. Found: C, 64.46; H, 4.60.
Compound 12: [α]_D ²⁰ +64.1 (c 0.32, CH₂Cl₂). ¹H NMR (300 MHz, CDCl₃): δ = 1.02 (s, 9 H), 1.18 (t, 3 H, J = 7.1 Hz), 2.05-2.30 (m, 2 H), 3.22 (dq, 1 H, J = 7.1, 9.5 Hz), 3.70 (m, 1 H), 4.23 (d, 1 H, J = 11.1 Hz), 4.35 (d, 1 H, J = 11.1 Hz), 4.44 (dd, 1 H, J = 3.2, 8.4 Hz), 4.67 (m, 1 H), 5.02 (d, 1 H, J = 6.7 Hz), 5.52 (dd, 1 H, J = 1.2, 9.8 Hz), 7.00-7.55 (m, 16 H), 7.67 (m, 2 H), 7.76 (m, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 15.1, 19.4, 26.9, 27.1, 31.4, 63.7, 74.4, 74.6, 75.1, 85.0, 98.7, 124.4, 127.2, 127.3, 127.4, 127.5, 127.7, 127.9, 128.1, 128.6, 129.4, 129.5, 129.6, 133.4, 134.0, 134.8, 136.0, 136.1, 138.6, 141.2. HRMS (ES): m/z calcd for C₃₈H₄₄O₄Si [M + Na]⁺: 615.2907; found: 615.2902.
Compound 13: [α]_D ²⁰ +45.9 (c 1.82, CH₂Cl₂). ¹H NMR (300 MHz, CDCl₃): δ = 1.06 (s, 9 H), 2.00 (ddd, 1 H, J = 3.7, 6.2, 18.1 Hz), 2.42 (m, 1 H), 3.58 (dd, 1 H, J = 2.5, 7.8 Hz), 3.90 (d, 1 H, J = 18.4 Hz), 3.95 (d, 1 H, J = 18.4 Hz), 4.76 (td, 1 H, J = 3.0, 12.6 Hz), 5.11 (d, 1 H, J = 7.8 Hz), 5.89 (dd, 1 H, J = 2.4, 9.8 Hz), 6.75 (ddd, 1 H, J = 2.1, 6.2, 9.8 Hz), 7.01 (m, 2 H), 7.19-7.68 (m, 18 H). ¹³C NMR (75 MHz, CDCl₃): δ = 19.4, 26.1, 27.1, 74.1, 74.5, 76.3, 83.9, 121.1, 127.3, 127.5, 127.6, 127.7, 127.8, 127.9, 128.0, 128.1, 128.2, 129.5, 129.7, 133.1, 133.5, 135.9, 136.0, 137.6, 141.3, 144.8, 163.5. HRMS (ES): m/z calcd for C₃₆H₃₈O₄Si [M + Na]⁺: 585.2437; found: 585.2434.