ACCEPTED MANUSCRIPT
4.5, 1.9, 1.9 Hz, 1H), 4.31 (d, J = 7.5 Hz, 1H), 3.79 (dd, J = 7.5, 4.5 Hz, 1H), 3.35 (d, J =14.0 Hz,
1H), 3.13 (dd, J = 15.3, 8.4 Hz, 1H), 3.02 (dd, J = 15.3, 8.4 Hz, 1H), 2.96 (d, J =14.0 Hz, 1H), 2.70
13
(d, J = 13.4 Hz, 1H), 2.27 (d, J = 13.4 Hz, 1H), 1.78-1.66 (m, 2H); C NMR (126 MHz, CDCl3): δ
169.9, 138.1, 137.7, 136.5, 134.6, 134.0, 133.4, 133.0, 131.9, 131.6, 130.1, 129.1, 129.0, 128.6,
128.19, 128.15, 127.2, 126.7, 126.6, 99.8, 73.6, 73.3, 68.0, 45.3, 43.6, 40.6, 40.4, 40.2, 31.2, 29.8. R-
30ia: 1H NMR (500 MHz, CDCl3, partial): δ 6.68-6.64 (m, 2H), 5.30 (d, J = 1.7 Hz, 1H), 4.77 (d, J =
1.7 Hz, 1H). FT-IR: 2986, 1732, 1264, 1335, 902, 704 cm-1; MS (ESI) m/z: 607.2 [M + Na]+; ESI-
HRMS Calcd for [M + Na]+ C35H33O4SClNa: 607.1686; found: 607.1715.
4.3.11.
(1S,4S,5R)-3,3-Dibenzyl-6,8-dioxabicyclo[3.2.1]octan-4-yl
3-(4-ethoxy-2,3,5,6-
tetrafluorophenyl)-3-(phenylthio)propanoate (30ja)
The reaction of 19j (100 mg, 1.0 equiv, 0.18 mmol) and PhSH (180 µL, 10.0 equiv, 1.80 mmol)
according to the general procedure gave 30ja as a colorless wax (110 mg, 89%, ratio isomers S:R
1
84:16). S-30ja: H NMR (500 MHz, CDCl3): δ 7.45-7.40 (m, 2H), 7.38-7.20 (m, 7H), 7.18-7.13 (m,
4H), 6.80-6.75 (m, 2H), 5.30 (d, J =1.7 Hz, 1H), 5.02 (dd, J = 8.5, 8.5 Hz, 1H), 4.85 (d, J =1.7 Hz,
1H), 4.39 (ddd, J = 4.8, 1.7, 1.7 Hz, 1H), 4.31 (d, J = 7.8 Hz, 1H), 4.12 (app. q, J = 7.2, 2H), 3.80
(dd, J = 7.8, 4.8 Hz, 1H), 3.37 (d, J =14.3 Hz, 1H), 3.26-3.16 (m, 2H), 3.01 (d, J =14.3 Hz, 1H), 2.46
(d, J = 13.8 Hz, 1H), 2.36 (d, J = 13.8 Hz, 1H), 1.81-1.71 (m, 2H), 1.31 (app. t, J = 7.2 Hz, 3H); 13C
NMR (126 MHz, CDCl3): δ 169.8, 148.2, 147.4, 137.8, 136.4, 134.0, 132.1, 131.8, 131.4, 129.3,
128.9, 128.8, 128.3, 128.2, 126.8, 126.7, 123.9, 99.7, 74.1, 73.3, 68.0, 48.9, 43.9, 40.7, 40.3, 40.2,
1
31.6. R-30ja: H NMR (500 MHz, CDCl3, partial): δ 6.71-6.67 (m, 2H), 4.81 (d, J = 1.9 Hz, 1H),
4.00 (app. q, J = 7.2 Hz, 1H). FT-IR: 2926, 1734, 1490, 1135, 1026, 902, 704 cm-1; MS (ESI) m/z:
689.3 [M + Na]+; ESI-HRMS Calcd for [M + Na]+ C37H34O5SF4Na: 689.1961; found: 689.1986.
4.3.12. (1S,4S,5R)-3,3-Dibenzyl-6,8-dioxabicyclo[3.2.1]octan-4-yl 3-(phenylthio)butanoate (30ka)
The reaction of 19k (100 mg, 1.0 equiv, 0.26 mmol) and PhSH (260 µL, 10.0 equiv, 2.60 mmol)
according to the general procedure gave 30ka as a colorless wax (118 mg, 92%, ratio isomers R:S
81:19). R-30ka: 1H NMR (500 MHz, CDCl3): δ 7.50-7.45 (m, 2H), 7.36-7.19 (m, 11H), 7.05-7.02 (m,
2H), 5.40 (d, J = 1.7 Hz, 1H), 4.98 (d, J = 1.7 Hz, 1H), 4.42 (ddd, J =4.9, 2.3, 2.3 Hz, 1H), 4.34 (d, J
= 7.7 Hz, 1H), 3.81 (dd, J = 7.7, 4.9 Hz, 1H), 3.74-3.70 (m, 1H), 3.40 (d, J = 15.1 Hz, 1H), 3.06 (d, J
= 15.1 Hz, 1H), 2.72 (d, J = 13.7 Hz, 1H), 2.70 (dd, J = 15.4, 7.2 Hz, 1H), 2.61 (dd, J = 15.4, 7.2 Hz,
13
1H), 2.41 (d, J = 13.7 Hz, 1H), 1.81-1.77 (m, 2H), 1.41 (d, J = 7.2 Hz, 3H); C NMR (126 MHz,
CDCl3): δ 170.7, 138.1, 136.8, 132.0, 131.9, 131.6, 129.2, 128.3, 128.2, 127.6, 126.8, 126.7, 99.9,
1
73.6, 73.4, 68.0, 44.0, 42.1, 40.4, 40.1, 39.4, 31.5, 29.8, 21.3. S-30ka: H NMR (500 MHz, CDCl3,
partial): δ 5.42 (d, J = 1.2 Hz, 1H), 3.21 (dd, J = 12.8 Hz, 1H), 1.40 (d, J = 7.1 Hz, 3H). FT-IR: 2923,
21