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33745716315
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note
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Kitahara has described a nonstereoselective route that affords all eight stereoisomers of preussin in a two-step sequence. The isomers were separated by preparative chiral HPLC. See ref 5.
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8
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33544456836
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For a recent review, see: Basler, B.; Brandes, S.; Spiegel, A.; Bach, T. Top. Curr. Chem. 2005, 243, 1.
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Basler, B.1
Brandes, S.2
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Bach, T.4
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9
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0001431750
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For early synthetic studies see: (a) Shimazaki, M.; Okazaki, F.; Nakajima, F.; Ishikawa, T.; Ohta, A. Heterocycles 1993, 36, 1823.
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(d) Huang, P.-Q.; Wu, T.-J.; Ruan, Y.-P. Org. Lett. 2003, 5, 4341.
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Huang, P.-Q.1
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33745730286
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Reference 9b
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Two strategies allow installation of the aryl moiety within 1-3 steps of the final target. Davis generated the C-2 benzyl group as the final step via reaction of lithium diphenyl cuprate with a pyrrolidinylmethyl iodide (40% yield, single diastereomer; 10 steps total, 9% overall yield). Bach employed a Paternò-Büchi reaction of benzaldehyde with a dihydropyrrole (4:1 dr, 53% yield after separation of diastereomers) followed by a two-step deprotection sequence to generate the benzyl substituent (39% over 3 steps; 9 steps total, 11% overall yield). See: (a) Reference 9b.
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19
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0033521583
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(b) Bach, T.; Brummerhop, H. Angew. Chem., Int. Ed. 1998, 37, 3400.
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Bach, T.1
Brummerhop, H.2
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0034675654
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To date, no analogues of preussin have been prepared that are modified on the aromatic ring. Bach has reported the synthesis of two analogues that differ in the nature of the C5 alkyl chain, and four analogues that differ in the nature of the C-3 substituent have been described in the patent literature. See: (a) Bach, T.; Brummerhop, H.; Harms, K. Chem. Eur. J. 2000, 6, 3838.
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Jpn. Kokai. Tokkyo Koho 2003277357, 2003
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(b) Suzuki, K.; Miike, N.; Kawamoto, E. Jpn. Kokai. Tokkyo Koho 2003277357, 2003.
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33645897192
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For a discussion of allylic strain related to the partial double bond character between the nitrogen atom and the carbonyl carbon in α-substituted amides and carbamates see: (a) Hoffmann, R. W. Chem. Rev. 1989, 89, 1841.
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33845278130
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33
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33745730290
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note
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Dpe-phos = bis(2-diphenylphosphinophenyl) ether.
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34
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0000194961
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The (-)-B-chlorodiisopinocampheylborane-mediated asymmetric aldol reaction between 2-undecanone and acrolein provided 7 in 78% yield and 48% ee, using Paterson's conditions. See: Paterson, I.; Goodman, J. M.; Lister, M. A.; Schumann, R. C.; McClure, C. K.; Norcross, R. D. Tetrahedron 1990, 46, 4663.
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Paterson, I.1
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Cogan, D.A.1
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36
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33745702258
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note
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1H NMR analysis.
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37
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0034697032
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Toujas, J.-L.; Toupet, L.; Vaultier, M. Tetrahedron 2000, 56, 2665.
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Toujas, J.-L.1
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Vaultier, M.3
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38
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33745702255
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note
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Use of high-purity starting material (>97% by NMR and GC) was essential to obtain high yields in reactions of electron-rich aryl bromides. Use of starting material with trace (ca 5%) impurities led to catalyst deactivation and formation of complex mixtures of products with these substrate combinations.
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