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The nonclassical subgroup is defined as acetogenins bearing a THP and/or a ring-hydroxylated THF moiety.
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For further details on SAR. see refs 2a,b and references therein.
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33644637773
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note
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For clarity, the chiral auxiliaries used are abbreviated: R ′ (1S,2R)-nor-8-phenylmenthyl: R″ = (1R,2S,5R)-8-phenylmenthyl.
-
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43
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33644636450
-
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note
-
For clarity, the chiral auxiliaries used are abbreviated: R ′ (1S,2R)-nor-8-phenylmenthyl: R″ = (1R,2S,5R)-8-phenylmenthyl.
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44
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33644651417
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note
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This trend was efficiently exploited in the hetero-Michael cyclizations of 18 and 21 as described in ref 18.
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46
-
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33644661687
-
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note
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Upon cleavage of the chiral auxiliary in the subsequent step, the relationship between the products becomes enantiomeric, thus preventing removal of the minor isomer until a further reagent controlled asymmetric transformation is carried out.
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47
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0026664290
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51
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33644661245
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note
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Procedure: To a stirred solution of chloroacetate 36 (31 mg, 0.032 mmol) in 1.5 mL of toluene was added a freshly prepared solution of water (1.17 μL, 0.065 mmol) and t-BuOK (9.7 μL, 1.0 M in THF) in 0.7 mL of toluene at 0 °C. The temperature was brought to room temperature over 1 h. The reaction was then quenched by addition of phosphate buffer pH 7 and subjected to the usual workup giving the cyclisized product 29 (18.3 mg, 65%).
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84986437005
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64
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33644657288
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note
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To simplify the determination of the diastereoselecitivty of the addition, the saturated aldehyde 85 was used as a model.
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65
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0002217612
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69
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33644656202
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note
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47
-
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70
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0033529735
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For mechanistic insight into the asymmetric HWE reaction see: Norrby, P.-O.; Brandt, P.; Rein, T. J. Org. Chem. 1999, 64, 5845-5852.
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33644651103
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-
note
-
This should be compared to a 54:46 (Z):(E) mixture using a 50:50 mixure of phosphonates 55 and 56; see footnote 20.
-
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72
-
-
33644655090
-
-
note
-
2OH could be recovered in 80% by bulb-to-bulb distillation of the reaction crude.
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73
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, pp. 11990-11991
-
-
Paquette, L.A.1
Backhaus, D.2
Braun, R.3
-
75
-
-
33644638193
-
-
note
-
47
-
-
-
-
76
-
-
20544445701
-
-
Kirkham, J. E. D.; Courtney, T. D. L.; Lee, V.; Baldwin, J. E. Tetrahedron 2005, 61, 7219-7232.
-
(2005)
Tetrahedron
, vol.61
, pp. 7219-7232
-
-
Kirkham, J.E.D.1
Courtney, T.D.L.2
Lee, V.3
Baldwin, J.E.4
-
77
-
-
0024463710
-
-
Ito, Y.; Kobayashi, Y.; Kawabata, T.; Takase, M.; Terashima, S. Tetrahedron 1989, 45, 5767-5790.
-
(1989)
Tetrahedron
, vol.45
, pp. 5767-5790
-
-
Ito, Y.1
Kobayashi, Y.2
Kawabata, T.3
Takase, M.4
Terashima, S.5
-
80
-
-
33644638046
-
-
note
-
63
-
-
-
-
81
-
-
0034090697
-
-
see also: (b) Yu, Q.; Wu, Y.; Wu, Y.-L.; Xia, L.-J.; Tang, M.-H. Chirality 2000, 12, 127-129.
-
(2000)
Chirality
, vol.12
, pp. 127-129
-
-
Yu, Q.1
Wu, Y.2
Wu, Y.-L.3
Xia, L.-J.4
Tang, M.-H.5
-
82
-
-
0343632337
-
-
(c) Duret, P.; Figadere, B.; Hocquemiller, R.; Cave, A. Tetrahedron Lett. 1997, 38, 8849-8852.
-
(1997)
Tetrahedron Lett.
, vol.38
, pp. 8849-8852
-
-
Duret, P.1
Figadere, B.2
Hocquemiller, R.3
Cave, A.4
-
83
-
-
0023612477
-
-
Hart, D. J.; Hong, W. P.; Hsu, L. Y. J. Org. Chem. 1987, 52, 4665-4673.
-
(1987)
J. Org. Chem.
, vol.52
, pp. 4665-4673
-
-
Hart, D.J.1
Hong, W.P.2
Hsu, L.Y.3
-
85
-
-
33644638623
-
-
note
-
One might speculate that the very low concentration used in this analysis would render the outcome sensitive to experimental error and impurities.
-
-
-
-
86
-
-
0347520940
-
-
Latypov, S.; Franck, X.; Jullian, J.-C.; Hocquemiller, R.; Figadere, B. Chem. Eur. J. 2002, 8, 5662-5666.
-
(2002)
Chem. Eur. J.
, vol.8
, pp. 5662-5666
-
-
Latypov, S.1
Franck, X.2
Jullian, J.-C.3
Hocquemiller, R.4
Figadere, B.5
-
87
-
-
0037041356
-
-
Amador, M.; Ariza, X.; Garcia, J.; Ortiz, J. Tetrahedron Lett. 2002, 43, 2691-2694.
-
(2002)
Tetrahedron Lett.
, vol.43
, pp. 2691-2694
-
-
Amador, M.1
Ariza, X.2
Garcia, J.3
Ortiz, J.4
-
88
-
-
33644638926
-
-
note
-
3N, 10.0 equiv; butenolide 77, 1.3 equiv; and aldehyde 50b, 1.0 equiv.
-
-
-
-
89
-
-
33644660906
-
-
note
-
1H NMR of the reaction crude. The isomers are separable by flash but were not identified. One might expect that this cyclization could be circumvented by reversing the order of reactions, starting with elimination of 78 and then performing a diimide reduction of the product.
-
-
-
-
91
-
-
33644658609
-
-
note
-
1H NMR spectrum after filtration through a short plug of silica to remove any remaining aldehyde.
-
-
-
-
92
-
-
33644656350
-
-
note
-
3N, 5.0 equiv.
-
-
-
-
93
-
-
33644647895
-
-
note
-
For further details, see Supporting Information.
-
-
-
-
94
-
-
0013582137
-
-
Prepared using a protocol similar to that used in: Hatakeyama, S.; Satoh, K.; Sakurai, K.; Takano, S. Tetrahedron Lett. 1987, 28, 2713-2716.
-
(1987)
Tetrahedron Lett.
, vol.28
, pp. 2713-2716
-
-
Hatakeyama, S.1
Satoh, K.2
Sakurai, K.3
Takano, S.4
-
95
-
-
33644647445
-
-
note
-
13C NMR (125 MHz) δ 164.1, 151.9, 128, 1, 125.3, 125.1, 123.7, 121.1, 76.3, 62.4 (qd, J = 19.6, 5.5 Hz), 62.3 (qd, J = 19.6, 5.5 Hz), 50.5, 39.5, 39.5, 33.4, (d, J = 14.4 Hz), 32.9, 30.0, 26.6, 25.8, 24.6, 22.1.
-
-
-
-
96
-
-
33644641486
-
-
Ph.D. Thesis, Tartu University, Estonia
-
See also: Vares, L. Ph.D. Thesis, Tartu University, Estonia, 2000.
-
(2000)
-
-
Vares, L.1
-
97
-
-
33644651983
-
-
note
-
Alternatively, the crude 16 obtained after filtration through a short plug of silica could be directly subjected to reduction/protective group migration. This protocol afforded 18 in 70% overall yield, based on 20.
-
-
-
-
98
-
-
33644638333
-
-
note
-
Due to the higher reactivity of aldehyde 50a compared to that of aldehyde 70, the reaction could be run at room temperature using standard inert techniques.
-
-
-
-
99
-
-
0000017001
-
-
For analytical data of 57 and 61, see: Pedersen, T. M.; Jensen, J. F.; Humble, R. E.; Rein, T.; Tanner, D.; Bodmann, K.; Reiser, O. Org. Lett. 2000, 2, 535-538.
-
(2000)
Org. Lett.
, vol.2
, pp. 535-538
-
-
Pedersen, T.M.1
Jensen, J.F.2
Humble, R.E.3
Rein, T.4
Tanner, D.5
Bodmann, K.6
Reiser, O.7
-
100
-
-
33644641058
-
-
note
-
Sealing the reaction vessel using a septum was not sufficient to prevent TMS-acetylene from escaping from the reaction.
-
-
-
-
101
-
-
33644654423
-
-
note
-
19F analysis of the corresponding (+)-and (-)-MTPA derivatives.
-
-
-
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