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8044224728
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Dedicated to our brilliant colleague and friend, Jim D. Bain, who died March 2, 1995, of leukemia
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Dedicated to our brilliant colleague and friend, Jim D. Bain, who died March 2, 1995, of leukemia.
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0024397415
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Calyculin, tautomycin, nodularin, microcystin-LR, okadaic acid, and cantharidin are all available from commercial sources
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Calyculin, tautomycin, nodularin, microcystin-LR, okadaic acid, and cantharidin are all available from commercial sources.
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For Isobe's total TM synthesis, see: (e) Ichikawa, Y.; Naganawa, A.; Isobe, M. Synlett. 1993, 737-738. (f) Ichikawa, Y.; Tsuboi, K.; Naganawa, A.; Isobe, M. Synlett. 1993, 907-908. (g) Naganawa, A.; Ichikawa, Y.; Isobe, M. Tetrahedron 1994, 50, 8969-8982. (h) Jiang, Y. M.; Ichikawa, Y.; Isobe, M. Synlett 1995, 3, 285-288. (i) Ichikawa, Y.; Tsuboi, K.; Jiang, Y.; Naganawa, A.; Isobe, M. Tetrahedron Lett. 1995, 36, 7101-7104. (j) Jiang, Y.; Isobe, M. Tetrahedron 1996, 52, 2877-2892.
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59
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For Isobe's total TM synthesis, see: (e) Ichikawa, Y.; Naganawa, A.; Isobe, M. Synlett. 1993, 737-738. (f) Ichikawa, Y.; Tsuboi, K.; Naganawa, A.; Isobe, M. Synlett. 1993, 907-908. (g) Naganawa, A.; Ichikawa, Y.; Isobe, M. Tetrahedron 1994, 50, 8969-8982. (h) Jiang, Y. M.; Ichikawa, Y.; Isobe, M. Synlett 1995, 3, 285-288. (i) Ichikawa, Y.; Tsuboi, K.; Jiang, Y.; Naganawa, A.; Isobe, M. Tetrahedron Lett. 1995, 36, 7101-7104. (j) Jiang, Y.; Isobe, M. Tetrahedron 1996, 52, 2877-2892.
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60
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85037469028
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For Isobe's total TM synthesis, see: (e) Ichikawa, Y.; Naganawa, A.; Isobe, M. Synlett. 1993, 737-738. (f) Ichikawa, Y.; Tsuboi, K.; Naganawa, A.; Isobe, M. Synlett. 1993, 907-908. (g) Naganawa, A.; Ichikawa, Y.; Isobe, M. Tetrahedron 1994, 50, 8969-8982. (h) Jiang, Y. M.; Ichikawa, Y.; Isobe, M. Synlett 1995, 3, 285-288. (i) Ichikawa, Y.; Tsuboi, K.; Jiang, Y.; Naganawa, A.; Isobe, M. Tetrahedron Lett. 1995, 36, 7101-7104. (j) Jiang, Y.; Isobe, M. Tetrahedron 1996, 52, 2877-2892.
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61
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For Isobe's total TM synthesis, see: (e) Ichikawa, Y.; Naganawa, A.; Isobe, M. Synlett. 1993, 737-738. (f) Ichikawa, Y.; Tsuboi, K.; Naganawa, A.; Isobe, M. Synlett. 1993, 907-908. (g) Naganawa, A.; Ichikawa, Y.; Isobe, M. Tetrahedron 1994, 50, 8969-8982. (h) Jiang, Y. M.; Ichikawa, Y.; Isobe, M. Synlett 1995, 3, 285-288. (i) Ichikawa, Y.; Tsuboi, K.; Jiang, Y.; Naganawa, A.; Isobe, M. Tetrahedron Lett. 1995, 36, 7101-7104. (j) Jiang, Y.; Isobe, M. Tetrahedron 1996, 52, 2877-2892.
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62
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For Isobe's total TM synthesis, see: (e) Ichikawa, Y.; Naganawa, A.; Isobe, M. Synlett. 1993, 737-738. (f) Ichikawa, Y.; Tsuboi, K.; Naganawa, A.; Isobe, M. Synlett. 1993, 907-908. (g) Naganawa, A.; Ichikawa, Y.; Isobe, M. Tetrahedron 1994, 50, 8969-8982. (h) Jiang, Y. M.; Ichikawa, Y.; Isobe, M. Synlett 1995, 3, 285-288. (i) Ichikawa, Y.; Tsuboi, K.; Jiang, Y.; Naganawa, A.; Isobe, M. Tetrahedron Lett. 1995, 36, 7101-7104. (j) Jiang, Y.; Isobe, M. Tetrahedron 1996, 52, 2877-2892.
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For partial TM syntheses, see: (k) Nakamura, S.-i.; Shibasaki, M. Tetrahedron Lett. 1994, 35, 4145-4148. (l) Maurer, K. W.; Armstrong, R. W. J. Org. Chem. 1996, 61, 3106-3116.
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For partial TM syntheses, see: (k) Nakamura, S.-i.; Shibasaki, M. Tetrahedron Lett. 1994, 35, 4145-4148. (l) Maurer, K. W.; Armstrong, R. W. J. Org. Chem. 1996, 61, 3106-3116.
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65
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33847804804
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This strategic coupling was also successfully demonstrated in Oikawa and Ichihara's tautomycin synthesis. Also see: (a) Mukaiyama, T.; Banno, K.; Narasaka, K. J. Am. Chem. Soc. 1974, 96, 7503-7509. (b) Mukaiyama, T. Org. React. 1982, 28, 203-331. (c) Reetz, M. T. Angew. Chem., Int. Ed. Engl. 1984, 23, 556-569. (d) Reetz, M. Acc. Chem. Res. 1993, 26, 462-468.
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This strategic coupling was also successfully demonstrated in Oikawa and Ichihara's tautomycin synthesis. Also see: (a) Mukaiyama, T.; Banno, K.; Narasaka, K. J. Am. Chem. Soc. 1974, 96, 7503-7509. (b) Mukaiyama, T. Org. React. 1982, 28, 203-331. (c) Reetz, M. T. Angew. Chem., Int. Ed. Engl. 1984, 23, 556-569. (d) Reetz, M. Acc. Chem. Res. 1993, 26, 462-468.
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Although (S)-citronellene is commercially available from Fluka, we prepared it from (S)-citronellol using the Chugaev method of Kocienski and Cernigliaro (J. Org. Chem. 1977, 42, 3622-3624) on a 200 g scale (50% yield). We wish to thank Takasago Ltd. for the generous gift of (S)-citronellol.
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1H NMR analysis of the Mosher ester using a racemic control. Dale, J. A.; Dull, D. L.; Mosher, H. S. J. Org. Chem. 1969, 34, 2543-2549. The relative and absolute stereochemistry was predicted using the Duthaler precedent but unambiguously determined using the following reaction sequence: Absolute stereochemistry was determined later in the synthesis by spectroscopic identity of a derivative of 14 with an authentic tautomycin intermediate degraded from the natural product (see ref 9a,b).
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We observed small (3-5%) amounts of retroaldolization upon quenching this reaction into a 0°C solution of 1 N HCl
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We observed small (3-5%) amounts of retroaldolization upon quenching this reaction into a 0°C solution of 1 N HCl.
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For use of a methoxyacetyl-substituted oxazolidinone in a syn aldol reaction, see: (b) Ku, T. W.; Kondrad, K. H.; Gleason, J. G. J. Org. Chem. 1989, 54, 3487-3491. (c) Andrus, M. B.; Schreiber, S. L. J. Am. Chem. Soc. 1993, 115, 10420-10421.
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Unambiguous stereochemical assignment of 19 was determined by X-ray crystallographic analysis of the TBS ether and confirms the Evan's precedent
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Unambiguous stereochemical assignment of 19 was determined by X-ray crystallographic analysis of the TBS ether and confirms the Evan's precedent.
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1H NMR).
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Dibenzylacetylene dicarboxylate was prepared from ADA using the procedure of Radell J.; Brodman, B. W.; Hirshfeld, A.; Bergman, E. D. J. Phys. Chem. 1965, 69, 928-932. Bis[2-(trimethylsilyl)ethyl]-acetylene dicarboxylate was prepared using the method of Charlton, J. L.; Chee, G.; McColeman, H. Can. J. Chem. 1995, 73, 1454-1462.
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Dibenzylacetylene dicarboxylate was prepared from ADA using the procedure of Radell J.; Brodman, B. W.; Hirshfeld, A.; Bergman, E. D. J. Phys. Chem. 1965, 69, 928-932. Bis[2-(trimethylsilyl)ethyl]-acetylene dicarboxylate was prepared using the method of Charlton, J. L.; Chee, G.; McColeman, H. Can. J. Chem. 1995, 73, 1454-1462.
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