Spiroketalization Reactions on a Carbohydrate Template

Abstract

Negishi and Stille coupling reactions of 3,4,6-tri-O-benzyl-2-(tri-n-butylstannyl)-d-glucal with (Z)-vinyl iodides provides access to functionalized spiroketals.

Stille reaction - spiro compounds - palladium - tin - cross-coupling

References and Notes

1

Present address: Glycoform Limited, Unit 44C, Milton Park, Abingdon, Oxon OX14 4RU, UK

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17 Confer: Boeckman RK. Charette AB. Asberom T. Johnston BH. J. Am. Chem. Soc.  1991,  113:  5337 

18

As indicated by D₂O quenching experiments.

19

Representative Spectroscopic Data. Compound 17: IR (film): ν_max = 3031, 2968, 2927, 1661, 1496, 1454, 1399, 1365, 1309, 1245, 1215, 1177, 1097, 1028, 989, 911, 851, 735, 698 cm^-1. ¹H NMR (300 MHz, C₆D₆): δ = 1.16 (3 H, d, J = 7.5 Hz, Me), 1.64 (1 H, br d dt, J = 18.0, 3.5 Hz, 3-H), 1.75 (1 H, br d, J = 18.0 Hz, 3-H), 1.77 (1 H, t, J = 12.0 Hz, 11_ax-H), 2.41 (1 H, dd, J = 12.5 Hz, 11_eq-H), 3.84 (1 H, dd, J = 11.0, 2.0 Hz, CH ₂ OBn), 3.90 (1 H, t, J = 9.0 Hz, 9-H), 3.95 (1 H, dd, J = 11.0, 5.0 Hz, CH ₂ OBn), 4.09-4.18 (1 H, m, 2-H), 4.20-4.26 (1 H, ddd, J = 10.0, 5.0, 2.0 Hz, 8-H), 4.35-4.44 (1 H, m, 10-H), 4.45-5.20 (6 H, m, 3 × CH ₂ Ph), 4.69-4.71 (2 H, m, 4-H, 5-H), 7.10-7.50 (15 H, m, Ar). ¹³C NMR (75 MHz, C₆D₆): δ = 21.13, 32.34, 40.62, 63.71, 70.12, 71.50, 72.56, 73.53, 75.08, 78.68, 78.97, 96.19, 127.44, 127.49, 127.54, 127.69, 127.89, 128.01, 128.33, 128.49, 129.94, 129.94, 139.28, 139.64, 139.73. MS (CI): m/z (%) 501 (20) [M + H]⁺. HRMS: m/z calcd for C₃₂H₃₇O₅: 501.2641. Found: 501.2640.
Mixture of 19 and 20 (19:20 = 1.5:1): IR (film): ν_max = 3030, 2918, 1657, 1606, 1579, 1496, 1477, 1454, 1395, 1365, 1259, 1209, 1098, 1001, 910, 736, 696 cm^-1.
Compound 19: ¹H NMR (300 MHz, CHCl₃): δ = 1.28 (3 H, d, J = 7 Hz, Me), 2.07-2.20 (2 H, m, 2 × 3-H), 3.70 (1 H, d, J = 4.0 Hz, 11_eq-H), 3.72-3.90 (4 H, m, 8-H, H-9, CH ₂ OBn), 3.92-4.10 (1 H, m, 2-H), 4.44-5.00 (6 H, m, 3 × CH ₂ Ph), 4.54 (1 H, dd, J = 10.0, 4.0 Hz, 10-H), 6.00-6.20 (1 H, m, 4-H), 6.68 (1 H, d, J = 10.0 Hz, 5-H), 7.10-7.60 (20 H, m, Ar).
Compound 20: ¹H NMR (300 MHz, CHCl₃): δ = 1.32 (3 H, d J = 7.0 Hz), 2.07-2.20 (2 H, m, 3-H), 3.42 (1 H, d, J = 11.0 Hz, 11_ax-H), 3.72-3.90 (4 H, m, H-8, H-9, CH ₂ OBn), 3.92-4.10 (1 H, m, 2-H), 4.19 (1 H, dd J = 11.0, 9.0 Hz, 10-H), 4.44-5.00 (5 H, m, OCH ₂ Ph), 5.15 (1 H, d, J = 10.0 Hz, OCH ₂ Ph), 5.74 (1 H, d, J = 10.0 Hz, 5-H), 6.00-6.20 (1 H, m, 4-H). ¹³C NMR (75 MHz, CHCl₃, mixture of 19 and 20): δ = 20.98, 21.01, 31.68, 32.03, 55.33, 64.23, 64.74, 68.95, 69.43, 71.33, 71.82, 72.27, 73.38, 73.48, 74.96, 75.07, 75.94, 76.45, 79.40, 79.92, 83.28, 97.75, 98.56, 126.59, 127.03, 127.38, 127.43, 127.49, 127.62, 127.69, 127.75, 127.90, 127.96, 128.19, 128.25, 128.32, 128.38, 128.45, 128.84, 129.00, 129.27, 129.61, 131.55, 131.75, 132.88, 133.54, 138.30, 138.41, 138.46, 138.62 ppm. MS (CI): m/z = 657 (57) [M + H]⁺. HRMS: m/z calcd for C₃₈H₄₀O₅ ⁸⁰Se: 656.2041. Found: 656.2050.
Compound 21: IR (film): ν_max = 3062, 3031, 2928, 1656, 1579, 1496, 1477, 1454, 1398, 1360, 1321, 1264, 1209, 1112, 1025, 910, 838, 785, 736, 697 cm^-1. ¹H NMR (300 MHz, CHCl₃): δ = 1.37 (3 H, d, J = 7.5 Hz, Me), 2.10 (1 H, dt, J = 18, 3-H), 2.43 (1 H, ddd, J = 18.0, 5.0, 2.0 Hz, 3-H), 3.55 (1 H, d, J = 12 Hz, 11_ax-H), 3.81 (5 H, m, 8-H, 9-H, 10-H, CH ₂ OBn), 4.44 (1 H, m, 2-H), 4.56-5.07 (6 H, m, 3 × CH ₂ Ph), 6.13 (1 H, d, J = 11.0 Hz, 4-H), 6.32 (1 H, dt, J = 11.0, 5.0 Hz, 5-H), 7.20-7.25 (20 H, m, Ar) ppm. ¹³C NMR (75 MHz): δ = 21.71, 30.82, 57.39, 69.43, 69.87, 73.35, 73.42, 74.91, 75.44, 80.12, 83.58, 97.67, 123.47, 126.88, 127.52, 127.60, 127.82, 127.99, 128.15, 128,26, 128.34, 128.48, 128.72, 128.94, 131.13, 131.66, 133.13, 138.16, 138.30, 138.49 ppm. MS (CI): m/z (%) 657 (32) [M + H]⁺. HRMS: m/z calcd for C₃₈H₄₀O₅ ⁸⁰Se: 656.2041. Found: 656.2042.

20 See: Deslongchamps P. Stereoelectronic Effects in Organic Chemistry   Pergamon; Oxford: 1983.  Chap. 2.

21

Confer ref. 22b.

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25c

This route promises to provide access to substrates such as 3 with greater efficiency than observed using Beau’s methodology. Beau’s route (that used in this study, see ref. 14b) requires recycling of i in order to achieve the throughput required for preparative-scale reactions (Scheme 6).

Scheme 6