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Volumn 50, Issue 9, 2011, Pages 2094-2097

On the macrocyclization of the erythromycin core: Preorganization is not required

Author keywords

Ci H oxidation; cyclization; erythromycin; lactonization; natural products

Indexed keywords

CI-H OXIDATION; ERYTHROMYCIN; LACTONIZATION; MACRO-CYCLIZATION; NATURAL PRODUCTS; OXIDATIVE CYCLIZATION; PREORGANIZATION; PROTECTING GROUP;

EID: 79951915978     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201007309     Document Type: Article
Times cited : (55)

References (51)
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    • Hydrogen bonding in acyclic 1,3-diols may induce a solution conformation analogous to that of acetonide protecting groups
    • Hydrogen bonding in acyclic 1,3-diols may induce a solution conformation analogous to that of acetonide protecting groups:, C. E. Anderson, D. K. Britt, S. Sangji, D. J. O'Leary, C. D. Anderson, S. D. Rychnovsky, Org. Lett. 2005, 7, 5721.
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    • Note
    • The use of sterically bulky cladinose and desosamine sugar residues at the C-3 and C-5 hydroxy groups were thought to reduce the conformational mobility along the C-1-C-8 subunit of the backbone and facilitate cyclization of erythromycinB precursors (Ref.[10b]). Given this, we anticipate the use of larger, more removable protecting groups than methyl ethers will not impede cyclizations.
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    • Streamlining synthesis by late-stage Ci-H oxidation
    • Streamlining synthesis by late-stage Ci-H oxidation
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    • for the first explicit demonstration of this concept, see
    • for the first explicit demonstration of this concept, see, K. J. Fraunhoffer, D. A. Bachovchin, M. C. White, Org. Lett. 2005, 7, 223
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    • Fraunhoffer, K.J.1    Bachovchin, D.A.2    White, M.C.3
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    • Ref.[6]
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    • Springer, Heidelberg,; for some elegant examples of late-stage Ci-H hydroxylation and amination, see
    • R. W. Hoffmann, in Elements of Synthesis Planning, Springer, Heidelberg, 2009; for some elegant examples of late-stage Ci-H hydroxylation and amination, see
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    • Hoffmann, R.W.1
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    • For branched intermolecular allylic oxidations, see
    • For branched intermolecular allylic oxidations, see
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    • Although in the original studies by Woodward etal. (Ref.[4]), acylation-based macrolactonization was effected by the Corey method (Ref.[2]), nearly all subsequent studies have used the Yamaguchi protocol (Refs.[5c,d,f-i, 6])
    • Although in the original studies by Woodward etal. (Ref.[4]), acylation-based macrolactonization was effected by the Corey method (Ref.[2]), nearly all subsequent studies have used the Yamaguchi protocol (Refs.[5c,d,f-i, 6]);, J. Inanaga, K. Hirata, H. Saeki, T. Katsuki, M. Yamaguchi, Bull. Chem. Soc. Jpn. 1979, 52, 1989.
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    • Allylic alcohol 5 (Scheme3) gave a comparable macrolactonization yield to that of an analogous saturated alcohol under identical Yamaguchi conditions (namely, 87 % and 86 %, respectively, Ref.[5g])
    • Allylic alcohol 5 (Scheme3) gave a comparable macrolactonization yield to that of an analogous saturated alcohol under identical Yamaguchi conditions (namely, 87 % and 86 %, respectively, Ref.[5g]).
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    • Note
    • It is clear that the polypropionate core of the erythromycins (6-dEB) does not require artificial preorganization for macrocyclization. While we cannot exclude the possibility that erythronolideB or A would require preorganization because of the presence of a C-6 and/or C-12 hydroxy group(s), the fact that linear precursors to erythronolideB, A, and 6-dEB have all been cyclized under comparable Yamaguchi conditions using the same cyclic biasing elements in the same positions, strongly suggests that they will continue to behave in a very similar manner to 6-dEB (see Ref.[5f,g,i]).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.