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The analogous cycloaddition reaction between Danishefsky's diene and 15 proceeds in 95% ee and 65% yield, see ref. [20].
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54
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32944479086
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note
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In our previous report of this reaction, we erroneously reported that ent-18 produced 17, see ref. [17a].
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32944478637
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note
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The enantiomeric excess of 17 was determined using a chiracel OD HPLC column.
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32944478356
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note
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4] (see ref. [20]) or in 93% ee and 74% yield using 18.
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67
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32944460195
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note
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We carried out DAFT calculations on the epoxidation of related sub-strates in an effort to better understand the relatively lower levels of selectivity in the epoxidation reactions of 21 and 23. The calculations indicated that both the level of asynchronicity of the formation of the C-O bonds and stereoelectronics were important. A. Orendt, S. W. Roberts, J. D. Rainier, unpublished results.
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0000091226
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We had previously observed that the amount of cyclic product was dependent upon the steric shielding of the ester. Related reactions have been reported, see ref. [16] and a) J. R. Stille, R. H. Grubbs, J. Am. Chem. Soc. 1986, 108, 855;
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d) K. C. Nicolaou, M. H. D. Postema, E. W. Yue, A. Nadin, J. Am. Chem. Soc. 1996, 118, 10335;
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85
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0034710476
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Both α- and β-C-glycosides can be generated from the corresponding anhydride by simply changing the nucleophile used, see ref. [16] and J. D. Rainier, J. M. Cox, Org. Lett. 2000, 2, 2707.
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Rainier, J.D.1
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86
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32944475067
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note
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Also unsuccessful were more conventional oxocarbenium ion couplings with allyl nucleophiles. For examples of this type of reaction, see refs. [28a-d]:
-
-
-
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88
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32944460194
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note
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Attempts to induce a related methyl migration failed.
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M. Ferrer, M. Gibert, Sánchez-F. Baeza, A. Messeguer, Tetrahedron Lett. 1996, 37, 3585.
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See references [28a-d] and a) R. E. Ireland, C. S. Wilcox, S. Thaisrivongs, N. R. Vanier, Can. J. Chem. 1979, 57, 1743;
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b) B. Fraser-Reid, R. D. Dawe, D. B. Tulshian, Can. J. Chem. 1979, 57, 1746;
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d) G. A. Wallace, R. W. Scott, C. H. Heathcock, J. Org. Chem. 2000, 65, 4145.
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G. Dujardin, S. Rossignol, E. Brown, Tetrahedron 1995, 36, 1653.
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Dujardin, G.1
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95
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32944465288
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note
-
Presently, it is not clear why this reaction failed to give C-glycoside products. We have successfully coupled other tri- and tetracyclic anhydrides with allyl nucleophiles.
-
-
-
-
96
-
-
32944470283
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-
note
-
We initially employed an ester having an acetal in place of the silyl ether. However, the Takai-Utimoto acyclic enol ether forming reaction with this substrate gave a substantial amount of eliminated material.
-
-
-
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98
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0033574384
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For other examples of this reduction see references [17] and K. Fujiwara, D. Awakura, M. Tsunashima, A. Nakamura, T. Honma, A. Murai, J. Org. Chem. 1999, 64, 2616;
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Fujiwara, K.1
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99
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1842739309
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superhydride gives direct addition products, see M. Inoue, S. Yamashita, A. Tatami, K. Miyazaki, M. Hirama, J. Org. Chem. 2004, 69, 2797.
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Inoue, M.1
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100
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0035936738
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3Al to an α-substituted anhydride resulted in the desired C-ketoside, see J. D. Rainier, S. P. Allwein, J. M. Cox, J. Org. Chem. 2001, 66, 1380.
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Rainier, J.D.1
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P. Lesimple, J.-M. Beau, G. Jaurand, P. Sinay, Tetrahedron Lett. 1986, 27, 6201.
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18244373174
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Subsequently, we showed that anhydride 78 underwent other coupling reactions with C-nucleophiles to give C-ketosides, see S. W. Roberts, J. D. Rainier, Org. Lett. 2005, 7, 1141.
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Roberts, S.W.1
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32944478491
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A C(25) TIPS ether performed similarly to 77 while a C(25) TES ether gave mixtures of C(23) diastereomers similar to 83, see ref. [49]
-
A C(25) TIPS ether performed similarly to 77 while a C(25) TES ether gave mixtures of C(23) diastereomers similar to 83, see ref. [49].
-
-
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106
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0034814443
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See reference [32] and M. S. Sanford, J. A. Love, R. H. Grubbs, J. Am. Chem. Soc. 2001, 123, 6543.
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Sanford, M.S.1
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0000559010
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For studies on the formation and reactivity of Fischer carbenes from enol ethers and 38, see a) J. Louie, R. H. Grubbs, Organometallics 2002, 21, 2153;
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Louie, J.1
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J. D. Winkler, M. B. Rouse, M. F. Greaney, S. J. Harrison, Y. T. Jeon, J. Am. Chem. Soc. 2002, 124, 9726.
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110
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32944465134
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manuscript in preparation
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Ab initio calculations were carried out at the DFT level: A. Orendt, S. A. Roberts, J. D. Rainier, manuscript in preparation.
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Orendt, A.1
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111
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32944458000
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See reference [12k, 1]
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See reference [12k, 1].
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112
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0003942864
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Wiley, New York
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See E. L. Eliel, S. H. Wilen, Stereochemistry of Organic Compounds, Wiley, New York, 1994, pp. 880-886.
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Eliel, E.L.1
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