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33747884493
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for an asymmetric variant of this methodology, see
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b) for an asymmetric variant of this methodology, see: B. M. Trost, R. N. Bream, J. Xu, Angew. Chem. 2006, 118, 3181-3184;
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34
-
-
56749145729
-
-
Successful metathesis cyclizations took place only when the Grubbs 2nd generation catalyst was used. All other metathesis catalysts gave no product.
-
Successful metathesis cyclizations took place only when the Grubbs 2nd generation catalyst was used. All other metathesis catalysts gave no product.
-
-
-
-
35
-
-
0038163433
-
-
The effects of titanium additives for metathesis reactions have previously been reported, but none are as dramatic as the example discussed herein. See also: a A. Fürstner, K. Langemann, J. Am. Chem. Soc. 1997, 119, 9130-9136;
-
The effects of titanium additives for metathesis reactions have previously been reported, but none are as dramatic as the example discussed herein. See also: a) A. Fürstner, K. Langemann, J. Am. Chem. Soc. 1997, 119, 9130-9136;
-
-
-
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36
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0035847196
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c) A. Fürstner, Angew. Chem. 2000, 112, 3140-3172;
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0001399412
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Angew. Chem. Int. Ed. 2000, 39, 3012-3043.
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39
-
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56749114054
-
-
Complete NMR spectroscopic analysis, including full proton and carbon assignments from HSQC and HMBC data, and stereochemical assignments from NOESY data, can be found in the Supporting Information
-
Complete NMR spectroscopic analysis, including full proton and carbon assignments from HSQC and HMBC data, and stereochemical assignments from NOESY data, can be found in the Supporting Information.
-
-
-
-
41
-
-
56749109322
-
-
Independently of this study, we have converted diol 28 into 22 in five steps (bisepoxidation, acetylation, dehydration, allylic oxidation, and oxidation).
-
Independently of this study, we have converted diol 28 into 22 in five steps (bisepoxidation, acetylation, dehydration, allylic oxidation, and oxidation).
-
-
-
-
42
-
-
56749147982
-
-
To further highlight the fine balance needed for a successful cyclization, it is worth noting that the correct C12-hydroxy isomer does not undergo ring-closing metathesis.
-
To further highlight the fine balance needed for a successful cyclization, it is worth noting that the correct C12-hydroxy isomer does not undergo ring-closing metathesis.
-
-
-
-
43
-
-
56749115570
-
-
The substrate-controlled reduction of the ketone can be explained by the geminal dimethyl group on the ring, which blocks the hydride delivery from what might otherwise be considered the less-hindered face
-
The substrate-controlled reduction of the ketone can be explained by the geminal dimethyl group on the ring, which blocks the hydride delivery from what might otherwise be considered the less-hindered face.
-
-
-
-
44
-
-
0027997412
-
-
S. V. Ley, J. Norman, W. P. Griffith, S. P. Marsden, Synthesis 1994, 639-666.
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, pp. 639-666
-
-
Ley, S.V.1
Norman, J.2
Griffith, W.P.3
Marsden, S.P.4
-
46
-
-
18744380352
-
-
b) A. B. Smith III, E. F. Mesaros, E. A. Meyer, J. Am. Chem. Soc. 2005, 127, 6948-6949.
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Smith III, A.B.1
Mesaros, E.F.2
Meyer, E.A.3
-
47
-
-
56749172189
-
-
Interestingly, the C9=C10 trisubstituted bond could be cleanly inverted to the cis epoxide using this same sequence after initially epoxidizing C5=C6. This bisepoxide was subjected to Tsuji's allylic transposition and readily underwent allylic oxidation.
-
Interestingly, the C9=C10 trisubstituted bond could be cleanly inverted to the cis epoxide using this same sequence after initially epoxidizing C5=C6. This bisepoxide was subjected to Tsuji's allylic transposition and readily underwent allylic oxidation.
-
-
-
-
49
-
-
56749124801
-
-
4]/TBHP, and Pd/C/TBHP.
-
4]/TBHP, and Pd/C/TBHP.
-
-
-
-
50
-
-
56749140481
-
-
All nonrigidified substrates failed to cyclize using any of the known ruthenium metathesis catalysts. Other diol diastereoisomers were also accessed and evaluated, but these also failed to cyclize
-
All nonrigidified substrates failed to cyclize using any of the known ruthenium metathesis catalysts. Other diol diastereoisomers were also accessed and evaluated, but these also failed to cyclize.
-
-
-
|