Stereoselective Total Syntheses of Insect Juvenile Hormones JH 0 and JH I

Abstract

Total syntheses of juvenile hormones JH 0 and JH I have been achieved by a new iterative enol tosylate homologation strategy.

Key words

juvenile hormone - acyclic terpenoid - enol tosylate - Negishi coupling reaction

• References and Notes

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• 9 (Z)-24 was transformed into the corresponding bromide A by a series of sequential transformations: i) the Negishi cross-coupling reaction of with Et₂Zn in the presence of 10 mol% of Pd(PPh₃)₄, ii) reduction to the corresponding allylic alcohol, and iii) bromination to the allyl borimide A. However, it was found to be volatile and easily evaporated under the reduced pressure to lower the product yield (ca. 30%)
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• 12 The olefin geometry was confirmed by NOE experiments of the synthetic JH 0 and JH I (see Supporting Information)

• The use of the unactivated enol tosylate in the cross-coupling reaction has been discussed, see:

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• 14 The optical purity was confirmed by the total synthesis of JH 0 and JH I, and comparison of the optical rotations of the synthetic natural products with those of authentic data shown in below
• 15 Analytical Data of JH 0 (1): [α]_D ¹⁸ +13.4 (c 0.8, MeOH) [lit. ^5d [α]_D + 13.8 (c 0.92, MeOH)]. ¹H NMR (400 MHz, CDCl₃): δ = 5.61 (s, 1 H), 5.10 (br, 1 H), 3.68 (s, 3 H), 2.71 (dd, J = 6.6, 5.6 Hz, 1 H), 2.18–2.03 (m, 10 H), 1.63–1.48 (m, 4 H), 1.27 (s, 3 H), 1.07 (t, J = 7.6 Hz, 3 H), 1.00 (t, J = 7.6 Hz, 3 H), 0.96 (t, J = 7.6 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 166.8, 165.7, 141.2, 123.1, 114.5, 64.6, 61.8, 50.7, 38.1, 33.3, 27.2, 25.8, 25.7, 25.3, 23.2, 21.6, 13.1, 12.9, 9.6. IR (neat): 2970, 2353, 1720, 1644, 1461, 1209, 1149, 761 cm^–1. HRMS–FAB: m/z calcd for C₁₉H₃₃O₃ [M + H]⁺: 309.2430; found: 309.2421
• 16 Analytical Data of JH I (2): [α]_D ¹⁸ +14.4 (c 0.98, MeOH) [lit.^5a,e [α]_D ^22.5 +14.5 (c 0.78, MeOH)]. ¹H NMR (400 MHz, CDCl₃): δ = 5.66 (d, J = 0.6 Hz 1 H), 5.08 (t, J = 6.3 Hz, 1 H), 3.68 (s, 3 H), 2.71 (dd, J = 7.2, 6.0 Hz, 1 H), 2.18–2.03 (m, 8 H), 2.16 (d, J = 0.6 Hz, 3 H), 1.63–1.48 (m, 4 H), 1.27 (s, 3 H), 0.99 (t, J = 7.2 Hz 3 H), 0.97 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 167.2, 159.9, 141.3, 122.9, 115.3, 64.6, 61.8, 50.8, 41.1, 33.3, 27.2, 25.8, 25.6, 23.1, 21.6, 18.8, 13.1, 9.7. IR (neat): 2968, 2360, 1720, 1650, 1457, 1125, 1149, 770 cm^–1. HRMS–FAB: m/z calcd for C₁₈H₃₁O₃ [M + H]⁺: 295.2273; found: 295.2270