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DOI: 10.1055/s-2008-1077965
Stereospecific Synthesis of Eight-Membered Polyhydroxy Carbocycles via TIBAL-Promoted Claisen Rearrangement
Publication History
Publication Date:
15 July 2008 (online)
Abstract
The stereoselective synthesis of novel eight-membered polyhydroxy carbocycles was achieved from d-glucose via mercuriocyclization and triisobutylaluminum (TIBAL)-promoted Claisen rearrangement. Along with rearrangement, TIBAL also promoted debenzylation and cycloaddition, and a 3,9-dioxa-bicyclo[3.3.1]nonane derivative was formed. The stereoselectivity of mercuriocyclization was attributed to the interaction between mecurio and vinyl moities, and this interaction also assisted the mercurio derivative to exist in an abnormal conformation. The configuration and/or conformation of intermediates and products were identified by NMR spectral analyses.
Key words
carbocycle - carbasugar - mercuriocyclization - TIBAL - Claisen rearrangement - debenzylation
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- Supporting Information
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References and Notes
Synthesis of 7
To
alkene 6 (1.30 g, 2.30 mmol) dissolved
in anhyd THF (20 mL) was added Hg(OAc)2 (0.73 g, 2.31
mmol) under argon. The reaction mixture was stirred and refluxed
for 10 h, then sat. aq KCl (1 mL) was added, stirred, and refluxed
for another 2 h, quenched by the addition of brine at r.t., and extracted
three times with EtOAc. Organic extracts were combined, dried by
Na2SO4, filtered, and evaporated. The residue
was purified by column chromatography on SiO2 (PE-EtOAc,
20:1) to give 7 as a colorless oil (1.85
g, 99.9%). ¹H NMR (400 MHz, CDCl3): δ = 7.33-7.18
(m, 20 H, arom. H), 5.96 (dd, J
7,8a = 11.0
Hz, J
7,8b = 17.5
Hz, 1 H, H-7), 5.23-5.27 (m, J
8a,7 = 11.0
Hz, J
8b,7 = 17.5
Hz, J
8a,8b = J
8b,8a = 1.5
Hz, 2 H, H-8a, H-8b), 4.66, 4.59 (dd, J = 11.5
Hz, 2 H, HCH2Ph), 4.57, 4.51 (dd, J = 12.0
Hz, 2 H, HCH2Ph), 4.35, 4.23 (dd, J = 12.0
Hz, 2 H, HCH2Ph), 4.42 (m, J
2,3 = 3.0
Hz, J
2,1a = 6.0
Hz, J
2,1b = 4.0
Hz, 1 H, H-2), 3.90 (t, J
4,3 = 3.0
Hz, J
4,5 = 4.0
Hz, 1 H, H-4), 3.87, 3.41 (dd, J = 8.5
Hz, 2 H, H-9a, H-9b), 3.67 (d, J
5,4 = 4.0
Hz, 1 H,
H-5), 3.16 (t, J
3,2 = 3.0
Hz, J
3,4 = 3.0
Hz, 1 H, H-3), 1.94 (dd, J
1a,2 = 6.0
Hz, J
1a,1b = 12.0
Hz, 1 H, H-1a), 1.65 (dd, J
1b,2 = 4.0
Hz, J
1b,1a = 12.0
Hz, 1 H, H-1b). ¹³C NMR (100 MHz, CDCl3): δ = 139.2
(C-7), 138.5, 138.4, 138.0, 137.3 (4 × Cipso),
129.1-127.5 (arom. C), 114.6 (C-8), 79.6 (C-6), 76.2 (C-3),
76.0 (C-5), 75.9 (C-9), 74.2 (C-4), 73.9, 73.7, 72.5, 72.1 (4 × CH2Ph),
67.4 (C-2), 31.6 (C-1). MS (ESI-TOF+): m/z = 818 [M + NH4]+,
823 [M + Na]+, 839 [M + K]+. Anal.
Calcd for C37H39O5HgCl: C, 55.57;
H, 4.92. Found: C, 55.83; H, 5.10.
Synthesis of 9
Compound 8 (559 mg, 0.81mmol) dissolved in anhyd
DMF (5 mL) was treated with NaH (60% in oil, 323 mg, 8.10 mmol)
under argon. The reaction mixture was stirred for 1 h at r.t., quenched
with MeOH, and concentrated. The residue was added H2O
and extracted with CH2Cl2. The organic extracts
were washed twice with brine, dried by Na2SO4, filtered,
and evaporated. The residue was purified by column chromatography
(PE-EtOAc-Et3N, 15:1:0.02) to yield 9 as a colorless oil (377 mg, 82.7%). ¹H
NMR (300 MHz, CDCl3): δ = 7.02-6.78
(m, 20 H, arom. H), 5.88 (dd, J
7,8a = 17.5
Hz, J
7,8b = 11.0
Hz, 1 H, H-7), 5.43 (ss, J
8a,7 = 17.5
Hz, J
8a,8b = 1.5
Hz, 1 H, H-8a), 4.88 (dd, J
8b,7 = 17.5
Hz, J
8b,8a = 1.5
Hz, 1 H, H-8b), 4.70 (d, J
1a,1b = 1.5
Hz, 1 H, H-1a), 4.66 (d, J
1b,1a = 1.5
Hz, 1 H,
H-1b), 4.52 (dd, J = 11.5
Hz, 2 H, HCH2Ph), 4.39 (dd, J = 11.5
Hz, 2 H, HCH2Ph), 4.35 (dd, J = 11.5
Hz, 2 H, HCH2Ph), 4.20 (dd, J = 11.5
Hz, 2 H, HCH2Ph), 3.81 (m, J
5,4 = 8.0
Hz, J
4,5 = 8.0
Hz, J
4,3 = 8.0
Hz, 2 H, H-5, H-4), 3.58 (dd, J = 10.0
Hz, 2 H, H-9a, H-9b), 3.34 (d, J
3,4 = 8.0 Hz,
1 H, H-3). ¹³C NMR (75 MHz, CDCl3): δ = 156.0
(C-2), 139.3 (C-7), 139.0, 138.8, 138.7, 138.5 (4 × Cipso),
128.6-127.7 (arom. C), 115.3 (C-8), 94.7 (C-1), 84.2 (C-6),
82.8 (C-3), 82.2 (C-5), 80.6 (C-4), 75.6 (C-9), 74.7, 73.9, 73.5, 71.1
(4 × CH2Ph). MS (ESI-TOF+): m/z = 585 [M + Na]+, 601 [M + K]+.
Anal. Calcd for C37H38O5: C, 78.98;
H, 6.81. Found: C, 78.80; H, 7.02.
Synthesis of 1
To
the solution of compound 9 (660 mg, 1.17
mmol) in toluene (20 mL) was added dropwise 1 M TIBAL (11.7 mL, 11.7
mmol) in toluene at r.t. under argon. The mixture was stirred at
80 ˚C for 2 h, cooled to 0 ˚C, and quenched with 20% aq
NaOH solution. The mixture was extracted with toluene, and the organic
layers were combined, dried with Na2SO4, and
concentrated. The residue was purified by column chromatography
(PE-acetone, 20:1) to give 1 as colorless
oil (571 mg, 86.5%). ¹H NMR (300 MHz,
CDCl3): δ = 7.32-7.18 (m,
20 H, arom. H), 6.02 (t, J
6,7a = J
6,7b = 8
Hz, 1 H, H-6), 4.73 (d, J
4,3 = 6
Hz, 1 H, H-4), 4.61 (dd, J = 12 Hz,
2 H, HCH2Ph), 4.58 (dd, J = 12
Hz, 2 H, HCH2Ph), 4.48 (dd, J = 12
Hz, 2 H, HCH2Ph), 4.33 (dd, J = 12
Hz, 2 H, HCH2Ph), 4.11 (t, J
1,2 = 7
Hz, J
1,8a = 7
Hz, 1 H, H-1), 4.00 (dd, J = 12
Hz, 2 H, H-9), 3.90 (t, J
3,2 = J
3,4 = 6
Hz, 1 H,
H-3), 3.63 (dd, J
2,3 = 6
Hz, J
2,1 = 7
Hz, 1 H, H-2), 3.39 (s, 1 H, OH), 2.42 (br, 1 H, H-7a), 2.22 (br,
1 H, H-7b), 2.04 (t, J
8b,8a = 13
Hz, 1 H, H-8b), 1.71 (m, J
8a,8b = 13
Hz, J
8a,1 = 7 Hz,
1 H, H-8a). ¹³C NMR (75 MHz, CDCl3): δ = 138.6, 138.4,
138.1, 138.1 (4 × Cipso),
134.2 (C-5), 131.4 (C-6), 128.4-127.4 (arom. C), 84.4 (C-3), 81.3
(C-2), 78.7 (C-4), 74.2, 72.5, 72.2, 71.2 (4 × CH2Ph),
70.4 (C-1), 32.9 (C-8), 21.3 (C-7). MS (ESI-TOF+): m/z = 565 [M + H]+,
582 [M + NH4]+,
587 [M + Na]+, 603 [M + K]+. Anal.
Calcd for C37H40O5: C, 78.69; H,
7.14. Found: C, 78.84; H, 6.91.
Compound 10:
white solid. ¹H NMR (500 MHz, CDCl3):
δ = 7.26-7.19
(m, 15 H, H-arom.), 5.74 (dd, J
10,11a = 18
Hz, J
10,11b = 11
Hz, 1 H, H-10), 5.26 (dd, J
11a,10 = 18
Hz, J
11a,11b = 2
Hz, 1 H, H-11a), 5.09 (dd, J
11b,10 = 11
Hz, J
11b,11a = 2
Hz, 1 H, H-11b), 4.87 (dd, J = 12
Hz, 2 H, HCH2Ph), 4.82 (dd, J = 12
Hz, 2 H, HCH2Ph), 4.66 (dd, J = 12
Hz, 2 H, HCH2Ph), 4.58 (t, J
7,6 = J
7,8 = 9
Hz, 1 H,
H-7), 4.13 (d, J
2a,2b = 12
Hz, 1 H, H-2a), 4.02 (d, J
4a,4b = 12 Hz,
1 H, H-4a), 3.79 (dd, J
6,5 = 5
Hz, J
6,7 = 9
Hz, 1 H, H-6), 3.75 (dd, J
5,6 = 5
Hz, J
5,4b = 3
Hz, 1 H, H-5), 3.54 (dd, J
4b,4a = 12
Hz, J
4b,5 = 3
Hz 1 H, H-4b), 3.39 (d, J
8,7 = 9
Hz, 1 H, H-8), 3.22 (d, J
2b,2a = 12
Hz, 1 H, H-2b). ¹³C NMR (125 MHz, CDCl3): δ = 139.0,
138.6, 138.3 (3 × Cipso),
136.8 (C-10), 128.4-127.4 (arom. C), 115.5 (C-11), 84.4
(C-8), 83.7 (C-7), 80.9 (C-6), 75.5, 75.3, 73.2 (3 × CH2Ph),
74.6 (C-1), 69.6 (C-5), 68.8 (C-2), 63.8 (C-4). MS (ESI-TOF+): m/z = 490 [M + NH4]+,
495 [M + Na]+, 511 [M + K]+. Anal.
Calcd for C37H40O5: C, 76.25; H,
6.83. Found: C, 76.50; H, 7.05.
Synthesis of 2
To
the solution of Ph3P (296 mg, 1.13 mmol) in anhyd THF (3
mL) previously cooled in an ice bath was added dropwise 2.2 M DEAD
in toluene (0.5 mL, 1.13 mmol) under argon. After 30 min, this solution
was added dropwise to the solution of compound 1 (254
mg, 0.45 mmol) and benzoic acid (100 mg, 0.82 mmol) in anhyd THF
under argon in an ice bath. The mixture was stirred for 30 min at
0 ˚C, then stirred at 45 ˚C for 3 h. When the
volatiles were removed, the residue was purified by column chromatography
(PE-acetone, 40:1) to yield 10 as
colorless oil (290 mg, 96.5%). Compound 10 (362
mg, 0.54 mmol) dissolved in MeOH (10 mL) was treated with K2CO3 (372
mg, 2.69 mmol) and stirred at r.t. for 12 h. The reaction mixture
was subsequently filtered and concentrated, and the residue was
purified by column chromatography (PE-acetone, 20:1) to
afford 2 as colorless oil (254 mg, 82.7%). ¹H
NMR (500 MHz, CDCl3): δ = 7.31-7.21
(m, 20 H, arom. H), 6.03 (t, J
6,7a = J
6,7b = 8.5 Hz,
1 H, H-6), 4.67 (dd, J = 12.0
Hz, 2 H, HCH2Ph), 4.62 (dd, J = 12.0
Hz, 2 H, HCH2Ph), 4.47 (dd, J = 12.0
Hz, 2 H, HCH2Ph), 4.43 (dd, J = 12.0
Hz, 2 H, HCH2Ph), 4.41 (m, J
2,1 = 2.5
Hz, J
2,3 = 6.0
Hz, 1 H, H-2), 4.07-3.98 (m, 3 H,
H-1, H-9a,
H-9b), 3.83 (t, J
3,2 = 6.0
Hz, J
3,4 = 5.0
Hz, 1 H,
H-3), 3.69 (d, J
4,3 = 5.0
Hz, 1 H, H-4), 2.36 (br, 1 H, H-7a), 2.10 (m, 1 H, H-7b), 2.00 (m,
1 H, H-8a), 1.70 (m, 1 H, H-8b). MS (ESI-TOF+): m/z = 565 [M + H]+,
582 [M + NH4]+, 587 [M + Na]+,
603 [M + K]+. Anal.
Calcd for C37H40O5: C, 78.69; H,
7.14. Found: C, 78.64; H, 7.02.