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Lee, J.H.2
Lee, B.W.3
Kim, J.H.4
Park, K.H.5
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7
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For some recent syntheses of ceramide/sphingolipids, see: (a) Jeong, L.-Y.; Lee, J. H.; Lee, B. W.; Kim, J. H.; Park, K. H. Bull. Korean Chem. Soc. 2003, 24, 617-622. (b) Milne, J. E.; Jarowicki, K.; Kocienski, P. J.; Alonso, J. Chem. Commun. 2002, 426-427. (c) Lees, W. J.; Gargano, J. M. Tetrahedron Lett. 2001, 42, 5845-5847. (d) Lee, J.-M.; Lim, H.-S.; Chung, S.-K. Tetrahedron: Asymmetry 2002, 13, 343-347. (e) Bittman, R.; Chun, J.; Li, G.; Byun, H.-S. Tetrahedron Lett. 2002, 43, 375-377.
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Milne, J.E.1
Jarowicki, K.2
Kocienski, P.J.3
Alonso, J.4
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8
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0035920888
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For some recent syntheses of ceramide/sphingolipids, see: (a) Jeong, L.-Y.; Lee, J. H.; Lee, B. W.; Kim, J. H.; Park, K. H. Bull. Korean Chem. Soc. 2003, 24, 617-622. (b) Milne, J. E.; Jarowicki, K.; Kocienski, P. J.; Alonso, J. Chem. Commun. 2002, 426-427. (c) Lees, W. J.; Gargano, J. M. Tetrahedron Lett. 2001, 42, 5845-5847. (d) Lee, J.-M.; Lim, H.-S.; Chung, S.-K. Tetrahedron: Asymmetry 2002, 13, 343-347. (e) Bittman, R.; Chun, J.; Li, G.; Byun, H.-S. Tetrahedron Lett. 2002, 43, 375-377.
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Gargano, J.M.2
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9
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0037155732
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For some recent syntheses of ceramide/sphingolipids, see: (a) Jeong, L.-Y.; Lee, J. H.; Lee, B. W.; Kim, J. H.; Park, K. H. Bull. Korean Chem. Soc. 2003, 24, 617-622. (b) Milne, J. E.; Jarowicki, K.; Kocienski, P. J.; Alonso, J. Chem. Commun. 2002, 426-427. (c) Lees, W. J.; Gargano, J. M. Tetrahedron Lett. 2001, 42, 5845-5847. (d) Lee, J.-M.; Lim, H.-S.; Chung, S.-K. Tetrahedron: Asymmetry 2002, 13, 343-347. (e) Bittman, R.; Chun, J.; Li, G.; Byun, H.-S. Tetrahedron Lett. 2002, 43, 375-377.
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Chung, S.-K.3
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For some recent syntheses of ceramide/sphingolipids, see: (a) Jeong, L.-Y.; Lee, J. H.; Lee, B. W.; Kim, J. H.; Park, K. H. Bull. Korean Chem. Soc. 2003, 24, 617-622. (b) Milne, J. E.; Jarowicki, K.; Kocienski, P. J.; Alonso, J. Chem. Commun. 2002, 426-427. (c) Lees, W. J.; Gargano, J. M. Tetrahedron Lett. 2001, 42, 5845-5847. (d) Lee, J.-M.; Lim, H.-S.; Chung, S.-K. Tetrahedron: Asymmetry 2002, 13, 343-347. (e) Bittman, R.; Chun, J.; Li, G.; Byun, H.-S. Tetrahedron Lett. 2002, 43, 375-377.
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Chun, J.2
Li, G.3
Byun, H.-S.4
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For recent reviews of sphingolipid syntheses, see: (f) Koskinen, P. M.; Koskinen, A. M. P. Synthesis 1998, 1075-1091. (g) Curfman, C.; Liotta, D. Methods Enzymol. 1999, 311, 391-457.
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4444232668
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note
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Gargano and Lees have reported the preparation of an orthogonally protected sphingosine with the main carbon chain already installed; See ref 3c.
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14
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2942752245
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During the preparation of this manuscript, we became aware of a report by Torssell and Somfai describing a cross metathesis approach to sphingosines using a different five-carbon building block. See: Torssell, S.; Somfai, P. Org. Biomol. Chem. 2004, 2, 1643-1646. A patent (WO 03/101937) by Rich and Bundle refers to olefin cross metathesis reactions of similar structures, but reduction to practice is not disclosed in the patent.
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0001318436
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During their synthesis of sphingolipids, Nugent and Hudlicky noted that reaction of azido aldehydes with Wittig reagents also resulted in reaction of the ylide at the azide functionality. See: Nugent, T.; Hudlicky, T. J. Org. Chem. 1998, 63, 510-520. We have found that careful addition of the ylide to the aldehyde at -78°C results in clean olefination, while higher temperatures give rise to products derived from both olefination and reaction at the azide.
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4444314394
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note
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The thiotrityl alkene was prepared from the known alkenol. Details are provided in Supporting Information.
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4444221010
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note
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The isolated yields for the cross metathesis reactions of the acetyl, palmitoyl, and benzoyl amides of 8 with hexadecene range from 71% to 92%. The pivaloyl amide undergoes cross metathesis with hexadecene less efficiently, affording the product in only 37% yield.
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