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The synthesis of the unnatural congener, (+)-normethyljatrophone, was achieved initially; see ref 8b. (diagram presented)
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Smith, A. B., III; Chen, K.; Robinson, D. J.; Laasko, L. M.; Hale, K. J. Formal Total Synthesis of FK506. Concise Construction of the C(10)-C(34) Segment via an Effective Coupling Tactic. Tetrahedron Lett. 1994, 35, 4271-4274.
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2942692494
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note
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Williams described the first use of HMPA as an additive for the lithiation of dithianes; see ref 27. Best conditions for lithiation entail dropwise addition of t-BuLi to a solution of the dithiane in THF/HMPA (5-10% v/v) at -78 °C, followed by gradual warming to -45 °C over 30 min.
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Smith, A. B., III; Chen, K.; Robinson, D. J.; Laasko, L. M.; Hale, K. J. Formal Total Synthesis of FK506. Concise Construction of the C(10)-C(34) Segment via an Effective Coupling Tactic. Tetrahedron Lett. 1994, 35, 4271-4274.
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(a) Smith, A. B., III; Friestad, G. K.; Barbosa, J.; Bertounesque, E.; Hull, K. G.; Iwashima, M.; Qui, Y.; Salvatore, B. A.; Spoors, G.; Duan, J. J.-W. Total Synthesis of (+)-Calyculin A and (-)-Calyculin B: Asymmetric Synthesis of the C(9-25) Spiroketal Dipropionate Subunit. J. Am. Chem. Soc. 1999, 121, 10468-10477.
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(b) Smith, A. B., III; Friestad, G. K.; Barbosa, J.; Bertounesque, E.; Duan, J. J.-W.; Hull, K. G.; Iwashima, M.; Qui, Y.; Spoors, G.; Salvatore, B. A. Total Synthesis of (+)-Calyculin A and (-)-Calyculin B: Cyanotetraene Construction, Asymmetric Synthesis of the C(26-37) Oxazole, Fragment Assembly, and Final Elaboration. J. Am. Chem. Soc. 1999, 121, 10478-10486.
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Work in our laboratories has demonstrated that the observed silyl migration is intramolecular; see ref 48.
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(a) Smith, A. B., III; Doughty, V. A.; Lin, Q. Y.; Zhuang, L. H.; McBriar, M. D.; Boldi, A. M.; Moser, W. H.; Murase, N. Nakayama, K.; Sobukawa, M.; The Spongistatins: Architecturally Complex Natural Products-Part One: A Formal Synthesis of (+)-Spongistatin 1 by Construction of an Advanced ABCD Fragment. Angew. Chem., Int. Ed. 2001, 40, 191-195.
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(b) Smith, A. B., III; Lin, Q. Y.; Doughty, V. A.; Zhuang, L. H.; McBriar, M. D.; Kerns, J. K.; Brook, C. S.; Murase, N.; Nakayama, K. The Spongistatins: Architecturally Complex Natural Products-Part Two: Synthesis of the C(29-51) Subunit, Fragment Assembly and Final Elaboration of (+)-Spongistatin 2. Angew. Chem., Int. Ed. 2001, 40, 196-199.
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Smith, A. B., III; Doughty, V. A.; Sfouggatakis, C.; Bennett, C. S.; Koyanagi, J.; Takeuchi, M. Spongistatin Synthetic Studies. An Efficient, Second-Generation Construction of an Advanced ABCD Intermediate. Org. Lett. 2002, 4, 783-786.
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While conversion of alcohols to the corresponding aldehydes or ketones is easily accomplished (e.g., Swern and Parikh-Doering oxidations), reliable conversion of an aldehyde to the corresponding acid, or derivative there of, in the presence of a dithiane is not well precedented.
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