1040
Vol.ꢀ61, No.ꢀ10
4.49–4.52ꢀ (m,ꢀ 1H),ꢀ 4.20–4.22ꢀ (m,ꢀ 1H),ꢀ 3.80–4.00ꢀ (m,ꢀ 6H),ꢀ d6) δ:ꢀ7.12–7.18ꢀ(m,ꢀ5H),ꢀ6.84ꢀ(s,ꢀ1H),ꢀ4.89ꢀ(d,ꢀJ=7.7ꢀHz,ꢀ1H),ꢀ
2.55ꢀ (q,ꢀ J=7.6ꢀHz,ꢀ 2H),ꢀ 1.15ꢀ (t,ꢀ J=7.6ꢀHz,ꢀ 3H),ꢀ 1.05–1.10ꢀ (m,ꢀ 4.21ꢀ (d,ꢀ J=9.7ꢀHz,ꢀ1H),ꢀ4.02–4.08ꢀ(m,ꢀ3H),ꢀ3.70–3.76ꢀ(m,ꢀ1H),ꢀ
21H),ꢀ1.03ꢀ(s,ꢀ9H),ꢀ0.96ꢀ(s,ꢀ9H).ꢀMSꢀ(APCI,ꢀm/z) 643 (M+ꢀH ) .
3.64–3.68ꢀ(m,ꢀ2H),ꢀ3.40–3.48ꢀ(m,ꢀ1H),ꢀ3.20–3.26ꢀ(m,ꢀ1H),ꢀ2.56ꢀ
(4aR,8R,8aR)-2,2-Di-tert-butyl-6-[2-(4-ethylbenzyl)-3- (q, J=7.6ꢀHz,ꢀ2H),ꢀ1.15ꢀ(t,ꢀJ=7.7ꢀHz,ꢀ3H),ꢀ1.04–1.09ꢀ(m,ꢀ21H),ꢀ
thienyl]-8-[(triisopropylsilyl)ꢀoxy]-4,4a,8,8a-tetrahydropyrano- 1.02ꢀ(s,ꢀ9H),ꢀ0.96ꢀ(s,ꢀ9H).ꢀMSꢀ(APCI,ꢀm/z) 678 (M+ꢀN H 4).
[3,2-d][1,3,2]ꢀdioxasilineꢀ (5d):ꢀ Theꢀ titledꢀ compoundꢀ wasꢀ pre-
(4aR,6S,7S,8R,8aR)-2,2-Di-tert-butyl-6-[4-(4-ethylbenzyl)-2-
pared in the same manner as described for 5a using 7d instead thienyl]-8-[(triisopropylsilyl)ꢀoxy]ꢀhexahydropyrano[3,2-d]-
of 7aꢀ inꢀ 53%ꢀ yieldꢀ asꢀ colorlessꢀ amorphousꢀ solid.ꢀ 1H-NMRꢀ [1,3,2]ꢀdioxasilin-7-olꢀ (6c):ꢀ Theꢀ titledꢀ compoundꢀ wasꢀ preparedꢀ
(300ꢀMHz,ꢀ CDCl3) δ:ꢀ 7.05–7.13ꢀ (m,ꢀ 4H),ꢀ 7.05ꢀ (d,ꢀ J=5.3ꢀHz,ꢀ in the same manner as described for 6a using 5c instead of
1H),ꢀ7.00ꢀ(d,ꢀJ=5.3ꢀHz,ꢀ1H),ꢀ4.88ꢀ(d,ꢀJ=2.2ꢀHz,ꢀ1H),ꢀ4.47ꢀ(dd,ꢀ 5aꢀinꢀ61%ꢀyieldꢀasꢀcolorlessꢀoil.ꢀ1H-NMRꢀ(500ꢀMHz,ꢀDMSO-
J=2.2,ꢀ 6.9ꢀHz,ꢀ 1H),ꢀ 4.25ꢀ (ABq,ꢀ J=16.3ꢀHz,ꢀ 1H),ꢀ 4.20ꢀ (ABq,ꢀ d6) δ:ꢀ7.03–7.17ꢀ(m,ꢀ5H),ꢀ6.86ꢀ(s,ꢀ1H),ꢀ5.04ꢀ(d,ꢀJ=6.9ꢀHz,ꢀ1H),ꢀ
J=16.3ꢀHz,ꢀ1H),ꢀ3.94–4.06ꢀ(m,ꢀ3H),ꢀ3.79–3.89ꢀ(m,ꢀ1H),ꢀ2.61ꢀ(q,ꢀ 4.44ꢀ(d,ꢀJ=9.5ꢀHz,ꢀ1H),ꢀ4.00–4.05ꢀ(m,ꢀ1H),ꢀ3.80–3.85ꢀ(m,ꢀ3H),ꢀ
J=7.7ꢀHz,ꢀ2H),ꢀ1.22ꢀ(t,ꢀJ=7.5ꢀHz,ꢀ3H),ꢀ1.04–1.12ꢀ(m,ꢀ21H),ꢀ0.99ꢀ 3.62–3.75ꢀ(m,ꢀ2H),ꢀ3.47–3.54ꢀ(m,ꢀ1H),ꢀ3.16–3.22ꢀ(m,ꢀ1H),ꢀ2.55ꢀ
(s,ꢀ9H),ꢀ0.85ꢀ(s,ꢀ9H).ꢀMSꢀ(APCI,ꢀm/z) 643 (M+ꢀH ) .
(4aR,8R,8aR)-2,2-Di-tert-butyl-6-[4-chloro-5-(4- 1.01ꢀ(s,ꢀ9H),ꢀ0.96ꢀ(s,ꢀ9H).ꢀMSꢀ(APCI,ꢀm/z) 678 (M+ꢀN H 4).
ethylbenzyl)-2-thienyl]-8-[(triisopropylsilyl)oꢀ xy]-4,4a,8,8a-
(4aR,6S,7S,8R,8aR)-2,2-Di-tert-butyl-6-[2-(4-ethylbenzyl)-3-
(q, J=7.6ꢀHz,ꢀ2H),ꢀ1.15ꢀ(t,ꢀJ=7.7ꢀHz,ꢀ3H),ꢀ1.05–1.08ꢀ(m,ꢀ21H),ꢀ
tetrahydropyrano[3,2-d][1,3,2]ꢀdioxasilineꢀ (5e):ꢀ Theꢀ titledꢀ thienyl]-8-[(triisopropylsilyl)ꢀoxy]ꢀhexahydropyrano[3,2-d]-
compound was prepared in the same manner as described for [1,3,2]ꢀdioxasilin-7-olꢀ (6d):ꢀ Theꢀ titledꢀ compoundꢀ wasꢀ preparedꢀ
5a using 7e instead of 7aꢀ inꢀ 68%ꢀ yieldꢀ asꢀ colorlessꢀ viscousꢀ in the same manner as described for 6a using 5d instead of 5a
oil.ꢀ1H-NMRꢀ(300ꢀMHz,ꢀCDCl3) δ:ꢀ7.13ꢀ(m,ꢀ4H),ꢀ6.93ꢀ(s,ꢀ1H),ꢀ inꢀ60%ꢀyieldꢀasꢀcolorlessꢀgum.ꢀ1H-NMRꢀ(300ꢀMHz,ꢀCDCl3) δ:ꢀ
5.05ꢀ(d,ꢀJ=2.5ꢀHz,ꢀ1H),ꢀ4.50ꢀ(dd,ꢀJ=2.4,ꢀ6.6ꢀHz,ꢀ1H),ꢀ4.23ꢀ(dd,ꢀ 7.10–7.18ꢀ (m,ꢀ 5H),ꢀ 7.00ꢀ (d,ꢀ J=5.3ꢀHz,ꢀ 1H),ꢀ 4.40ꢀ (d,ꢀ J=9.7ꢀHz,ꢀ
J=4.9,ꢀ10.2ꢀHz,ꢀ1H),ꢀ4.04ꢀ(s,ꢀ2H),ꢀ3.90–4.08ꢀ(m,ꢀ3H),ꢀ2.62ꢀ(q,ꢀ 1H),ꢀ 4.16ꢀ (ABq,ꢀ J=16.1ꢀHz,ꢀ 2H),ꢀ 4.12ꢀ (dd,ꢀ J=5.0,ꢀ 10.3ꢀHz,ꢀ
J=7.7ꢀHz,ꢀ2H),ꢀ1.22ꢀ(t,ꢀJ=7.7ꢀHz,ꢀ3H),ꢀ1.08–1.14ꢀ(m,ꢀ21H),ꢀ1.06ꢀ 1H),ꢀ 3.74ꢀ (m,ꢀ 3H),ꢀ 3.58ꢀ (ddd,ꢀ J=2.9,ꢀ 8.2,ꢀ 10.6ꢀHz,ꢀ 1H),ꢀ 3.44ꢀ
(s,ꢀ9H),ꢀ0.98ꢀ(s,ꢀ9H).ꢀMSꢀ(ESI,ꢀm/z) 677/679 (M+ꢀH ) .
(ddd, J=4.9,ꢀ8.7,ꢀ10.0ꢀHz,ꢀ1H),ꢀ2.62ꢀ(q,ꢀJ=7.5ꢀHz,ꢀ2H),ꢀ1.90ꢀ(d,ꢀ
(4aR,8R,8aR)-2,2-Di-tert-butyl-6-[5-chloro-4-(4- J=2.9ꢀHz,ꢀ1H),ꢀ1.22ꢀ(t,ꢀJ=7.5ꢀHz,ꢀ3H),ꢀ1.10–1.14ꢀ(m,ꢀ21H),ꢀ1.06ꢀ
ethylbenzyl)-2-thienyl]-8-[(triisopropylsilyl)ꢀoxy]-4,4a,8,8a- (s,ꢀ9H),ꢀ1.01ꢀ(s,ꢀ9H).ꢀMSꢀ(APCI,ꢀm/z) 678 (M+ꢀN H 4).
tetrahydropyrano[3,2-d][1,3,2]ꢀdioxasilineꢀ (5f):ꢀ Theꢀ titledꢀ
(4aR,6S,7S,8R,8aR)-2,2-Di-tert-butyl-6-[4-chloro-5-
compound was prepared in the same manner as described (4-ethylbenzyl)-2-thienyl]-8-[(triisopropylsilyl)ꢀoxy]-
for 5a using 7f instead of 7aꢀ inꢀ 59%ꢀ yieldꢀ asꢀ colorlessꢀ oil.ꢀ hexahydropyrano[3,2-d][1,3,2]ꢀdioxasilin-7-olꢀ (6e):ꢀ Theꢀ titledꢀ
1H-NMRꢀ(300ꢀMHz,ꢀCDCl3) δ:ꢀ7.12ꢀ(d,ꢀJ=8.4ꢀHz,ꢀ2H),ꢀ7.07ꢀ(d,ꢀ compound was prepared in the same manner as described for
J=8.3ꢀHz,ꢀ2H),ꢀ6.76ꢀ(s,ꢀ1H),ꢀ5.00ꢀ(d,ꢀJ=2.5ꢀHz,ꢀ1H),ꢀ4.49ꢀ(dd,ꢀ 6a using 5e instead of 5aꢀinꢀ46%ꢀyieldꢀasꢀcolorlessꢀviscousꢀoil.ꢀ
J=2.4,ꢀ 6.6ꢀHz,ꢀ 1H),ꢀ 4.22ꢀ (dd,ꢀ J=4.8,ꢀ 10.4ꢀHz,ꢀ 1H),ꢀ 3.98–4.06ꢀ 1H-NMRꢀ (500ꢀMHz,ꢀ DMSO-d6) δ:ꢀ 7.14–7.16ꢀ (m,ꢀ 4H),ꢀ 6.94ꢀ (s,ꢀ
(m,ꢀ 2H),ꢀ 3.92ꢀ (dd,ꢀ J=4.6,ꢀ 9.9ꢀHz,ꢀ 1H),ꢀ 3.83ꢀ (s,ꢀ 2H),ꢀ 2.60ꢀ (q,ꢀ 1H),ꢀ5.22ꢀ(d,ꢀJ=7.6ꢀHz,ꢀ1H),ꢀ4.43ꢀ(d,ꢀJ=9.6ꢀHz,ꢀ1H),ꢀ4.04ꢀ(dd,ꢀ
J=7.7ꢀHz,ꢀ2H),ꢀ1.22ꢀ(t,ꢀJ=7.7ꢀHz,ꢀ3H),ꢀ1.08–1.13ꢀ(m,ꢀ21H),ꢀ1.05ꢀ J=4.8,ꢀ10.1ꢀHz,ꢀ1H),ꢀ3.80ꢀ(Abq,ꢀJ=16.0ꢀHz,ꢀ2H),ꢀ3.60–3.73ꢀ(m,ꢀ
(s,ꢀ9H),ꢀ0.98ꢀ(s,ꢀ9H).ꢀMSꢀ(ESI,ꢀm/z) 677/679 (M+ꢀH ) .
3H),ꢀ3.49–3.55ꢀ(m,ꢀ1H),ꢀ3.10–3.15ꢀ(m,ꢀ1H),ꢀ2.57ꢀ(q,ꢀJ=7.6ꢀHz,ꢀ
Typical Experimental Procedure for the Synthesis of 2H),ꢀ 1.16ꢀ (t,ꢀ J=7.7ꢀHz,ꢀ 3H),ꢀ 1.05–1.08ꢀ (m,ꢀ 21H),ꢀ 1.00ꢀ (s,ꢀ 9H),ꢀ
β-d-Glucopyranosyl Derivatives (4aR,6S,7S,8R,8aR)-2,2-Di- 0.96ꢀ(s,ꢀ9H).ꢀMSꢀ(APCI,ꢀm/z) 712/714 (M+ꢀN H 4).
tert-butyl-6-[5-(4-ethylbenzyl)-3-thienyl]-8-[(triisopropylsilyl)-
(4aR,6S,7S,8R,8aR)-2,2-Di-tert-butyl-6-[5-chloro-4-
oxy]ꢀhexahydropyrano[3,2-d][1,3,2]ꢀdioxasilin-7-olꢀ(6a):ꢀToꢀaꢀso- (4-ethylbenzyl)-2-thienyl]-8-[(triisopropylsilyl)ꢀoxy]-
lution of compound 5aꢀ(385ꢀmg,ꢀ0.60ꢀmmol)ꢀinꢀtetrahydrofuranꢀ hexahydropyrano[3,2-d][1,3,2]ꢀdioxasilin-7-olꢀ (6f):ꢀ Theꢀ titledꢀ
(THF)ꢀ (5ꢀmL)ꢀ wasꢀ addedꢀ borane-tetrahydrofuranꢀ complexꢀ compound was prepared in the same manner as described for
(1.0ꢀMꢀ inꢀ THF,ꢀ 2.12ꢀmL,ꢀ 2.40ꢀmmol)ꢀ dropwiseꢀ atꢀ 0°C.ꢀ Afterꢀ 6a using 5f instead of 5aꢀinꢀ37%ꢀyieldꢀasꢀcolorlessꢀviscousꢀoil.ꢀ
beingꢀstirredꢀatꢀ0°Cꢀforꢀovernight,ꢀtheꢀmixtureꢀwasꢀaddedꢀ30%ꢀ 1H-NMRꢀ (500ꢀMHz,ꢀ DMSO-d6) δ:ꢀ 7.09–7.15ꢀ (m,ꢀ 4H),ꢀ 6.81ꢀ (s,ꢀ
aqueous hydrogen peroxide (5mL) and 3N aqueous sodium 1H),ꢀ5.20ꢀ(d,ꢀJ=7.7ꢀHz,ꢀ1H),ꢀ4.41ꢀ(d,ꢀJ=9.5ꢀHz,ꢀ1H),ꢀ4.04ꢀ(dd,ꢀ
hydroxideꢀ (5ꢀmL),ꢀ andꢀ stirredꢀ atꢀ 0°Cꢀ forꢀ 4ꢀh.ꢀ Theꢀ reactionꢀ J=4.9,ꢀ10.0ꢀHz,ꢀ1H),ꢀ3.80ꢀ(Abq,ꢀJ=15.1ꢀHz,ꢀ2H),ꢀ3.68–3.74ꢀ(m,ꢀ
mixture was extracted with Et2O, washed with brine, dried 1H),ꢀ3.60–3.68ꢀ(m,ꢀ1H),ꢀ3.49–3.54ꢀ(m,ꢀ1H),ꢀ3.36–3.42ꢀ(m,ꢀ1H),ꢀ
overꢀsodiumꢀsulfate,ꢀandꢀfiltered.ꢀTheꢀfiltrateꢀwasꢀconcentratedꢀ 3.09–3.16ꢀ (m,ꢀ 1H),ꢀ 2.55ꢀ (q,ꢀ J=7.5ꢀHz,ꢀ 2H),ꢀ 1.15ꢀ (t,ꢀ J=7.5ꢀHz,ꢀ
andꢀ dried,ꢀ thenꢀ theꢀ crudeꢀ materialꢀ wasꢀ purifiedꢀ byꢀ silicaꢀ gelꢀ 3H),ꢀ1.04–1.10ꢀ(m,ꢀ21H),ꢀ1.00ꢀ(s,ꢀ9H),ꢀ0.95ꢀ(s,ꢀ9H).ꢀMSꢀ(APCI,ꢀ
column chromatography (hexane–AcOEt=ꢀ100ꢀ:ꢀ0–97ꢀ:ꢀ3)ꢀ toꢀ m/z) 712/714 (M+ꢀN H 4).
give compound 6aꢀ(192ꢀmg,ꢀ42%)ꢀasꢀcolorlessꢀsyrup.ꢀ1H-NMRꢀ
Typical Experimental Procedure for the Synthesis of
(300ꢀMHz,ꢀ CDCl3) δ:ꢀ 7.13–7.16ꢀ (m,ꢀ 4H),ꢀ 7.10ꢀ (d,ꢀ J=0.9ꢀHz,ꢀ 1-Aryl-β-d-glucopyranoses (1S)-1,5-Anhydro-1-[5-(4-ethyl-
1H),ꢀ6.82ꢀ(d,ꢀJ=1.3ꢀHz,ꢀ1H),ꢀ4.26ꢀ(d,ꢀJ=9.5ꢀHz,ꢀ1H),ꢀ4.17ꢀ(dd,ꢀ benzyl)-3-thienyl]-D-glucitol (3a):ꢀ Toꢀ aꢀ solutionꢀ ofꢀ compoundꢀ
J=4.9,ꢀ10.1ꢀHz,ꢀ1H),ꢀ4.07ꢀ(s,ꢀ2H),ꢀ3.74–3.91ꢀ(m,ꢀ3H),ꢀ3.44–3.53ꢀ 6aꢀ(192ꢀmg,ꢀ0.29ꢀmmol)ꢀinꢀTHFꢀ(5ꢀmL)ꢀwasꢀaddedꢀTBAFꢀ(1.0ꢀM
(m,ꢀ2H),ꢀ2.63ꢀ(q,ꢀJ=7.5ꢀHz,ꢀ2H),ꢀ2.03ꢀ(d,ꢀJ=2.8ꢀHz,ꢀ1H),ꢀ1.22ꢀ inꢀ THF,ꢀ 1.45ꢀmL,ꢀ 1.45ꢀmmol)ꢀ dropwise,ꢀ thenꢀ theꢀ mixtureꢀ wasꢀ
(t, J=7.5ꢀHz,ꢀ 3H),ꢀ 1.09–1.14ꢀ (m,ꢀ 21H),ꢀ 1.06ꢀ (s,ꢀ 9H),ꢀ 1.00ꢀ (s,ꢀ stirredꢀ atꢀ 60°Cꢀ forꢀ 3ꢀh.ꢀ Theꢀ mixtureꢀ wasꢀ concentratedꢀ andꢀ
9H).ꢀMSꢀ(APCI,ꢀm/z) 678 (M+ꢀN H 4).
dried,ꢀ thenꢀ theꢀ crudeꢀ materialꢀ wasꢀ purifiedꢀ byꢀ silicaꢀ gelꢀ col-
(4aR,6S,7S,8R,8aR)-2,2-Di-tert-butyl-6-[5-(4-ethylbenzyl)-2- umnꢀ chromatographyꢀ (CHCl3–MeOH=ꢀ100ꢀ:ꢀ0–90ꢀ:ꢀ10)ꢀ toꢀ giveꢀ
thienyl]-8-[(triisopropylsilyl)ꢀoxy]ꢀhexahydropyrano[3,2-d]- compound 3aꢀ (60ꢀmg,ꢀ 57%)ꢀ asꢀ aꢀ colorlessꢀ powder.ꢀ 1H-NMRꢀ
[1,3,2]ꢀdioxasilin-7-olꢀ (6b):ꢀ Theꢀ titledꢀ compoundꢀ wasꢀ preparedꢀ (500ꢀMHz,ꢀDMSO-d6+D2O) δ:ꢀ7.18ꢀ(d,ꢀJ=8.1ꢀHz,ꢀ2H),ꢀ7.17ꢀ(s,ꢀ
in the same manner as described for 6a using 5b instead of 1H),ꢀ 7.14ꢀ (d,ꢀ J=8.0ꢀHz,ꢀ 2H),ꢀ 6.86ꢀ (s,ꢀ 1H),ꢀ 4.05ꢀ (s,ꢀ 2H),ꢀ 4.02ꢀ
5aꢀinꢀ66%ꢀyieldꢀasꢀcolorlessꢀoil.ꢀ1H-NMRꢀ(500ꢀMHz,ꢀDMSO- (d, J=9.3ꢀHz,ꢀ 1H),ꢀ 3.66ꢀ (d,ꢀ J=11.7ꢀHz,ꢀ 1H),ꢀ 3.41ꢀ (dd,ꢀ J=5.9,ꢀ