Recent advances in the chemistry of macroline, sarpagine and ajmaline-related indole alkaloids

Lewis, Simon E.

doi:10.1016/j.tet.2006.06.017

Cited by 89 publications

(33 citation statements)

References 94 publications

(86 reference statements)

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“…Sarpagine alkaloids can be converted to macroline 19 by a retro-Michael reaction or a Hoffmann elimination 18 reaction of the N b -methyl intermediate of 18a/b , as demonstrated by LeQuesne et al 19 and latter confirmed in Milwaukee, 20 whereas a biogenetic connection between the sarpagine and the ajmaline alkaloids was confirmed by conversion of 16-epivellosimine 20 into vinorine 21 by Stöckigt et al (Scheme 1). 21 …”

Section: Introductionmentioning

confidence: 87%

General Strategy for Synthesis of C-19 Methyl-Substituted Sarpagine/Macroline/Ajmaline Indole Alkaloids Including Total Synthesis of 19(S),20(R)-Dihydroperaksine, 19(S),20(R)-Dihydroperaksine-17-al, and Peraksine

Edwankar

Deschamps

et al. 2014

J. Org. Chem.

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A detailed account of the development of a general strategy for synthesis of the C-19 methyl-substituted alkaloids including total synthesis of 19(S),20(R)-dihydroperaksine-17-al (1), 19(S),20(R)-dihydroperaksine (2), and peraksine (6) is presented. Efforts directed toward the total synthesis of macrosalhine chloride (5) are also reported. Important to success is the sequence of chemical reactions which include a critical haloboration reaction, regioselective hydroboration, and controlled oxidation (to provide sensitive enolizable aldehydes at C-20). In addition, the all-important Pd-catalyzed α-vinylation reaction has been extended to a chiral C-19 alkyl-substituted substrate for the first time. Synthesis of the advanced intermediate 64 completes an improved formal total synthesis of talcarpine (26) and provides a starting point for synthesis of macroline-related alkaloids 27–31. Similarly, extension of this synthetic strategy in the ring A oxygenated series should provide easy access to the northern hemisphere 32b of the bisindoles angustricraline, alstocraline, and foliacraline (Figure 4).

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Section: Introductionmentioning

confidence: 87%

General Strategy for Synthesis of C-19 Methyl-Substituted Sarpagine/Macroline/Ajmaline Indole Alkaloids Including Total Synthesis of 19(S),20(R)-Dihydroperaksine, 19(S),20(R)-Dihydroperaksine-17-al, and Peraksine

Edwankar

Deschamps

et al. 2014

J. Org. Chem.

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“…The indole ring system is incorporated into a vast number of structurally diverse biologically active natural and synthetic compounds [147][148][149][150][151][152][153][154][155][156][157]. Consequently, the indole ring system has become an essential, or so called privileged, structural motif in many pharmaceutical agents [156,158].…”

Section: Indolesmentioning

confidence: 99%

Transition Metal‐Catalyzed Synthesis of Fused Five‐Membered Aromatic Heterocycles

Dudnik¹,

Gevorgyan²

2010

Catalyzed Carbon‐Heteroatom Bond Formation

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“…These compounds are characterized by a cycloocta [b]indole scaffold and often highly complex structures. [7] Interest in these alkaloids originated from folk tales that described the medicinal properties of the producing plants. To date, more than 100 macroline natural products have been elucidated.…”

Section: Introductionmentioning

confidence: 99%

“…Cook and co-workers developed an elegant methodology for the stereospecific generation of this scaffold in solution-phase chemistry and demonstrated its feasibility in numerous total syntheses of macroline-based natural products. [7,13] Their approach is based on selective isomerization and a subsequent ring-closing reaction of a trans-tetrahydrocarboline moiety, which is derived from a stereoselective Pictet-Spengler reaction. To steer this reaction stereoselectively, a directing group, usually a benzyl moiety, is introduced at the amino group of a chiral tryptophan residue, thus resulting in a high trans stereoselection during the Pictet-Spengler reaction.…”

Section: Introductionmentioning

confidence: 99%

Biology‐Oriented Combined Solid‐ and Solution‐Phase Synthesis of a Macroline‐Like Compound Collection

Wilk

Nören‐Müller

Kaiser

et al. 2009

Chemistry A European J

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Macrolines constitute a class of natural products that has more than 100 members and displays diverse biological activities. These compounds feature a cycloocta[b]indole scaffold that represents an interesting target structure for biology-oriented synthesis (BIOS). We have presented a solid-phase synthesis of isomerically pure cycloocta[b]indoles by employing the Pictet-Spengler reaction and the Dieckmann cyclization as key steps. The scope of this reaction sequence was investigated in more detail by using various additional diversification procedures, such as Pd-catalyzed Sonogashira or Suzuki couplings on a solid phase, thus allowing, for example, the generation of 10-substituted cycloocta[b]indole derivatives. Finally, solution-phase decoration of the cycloocta[b]indole skeleton by reduction and saponification was evaluated, thereby further extending the scope of the solid-phase synthesis.

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Recent advances in the chemistry of macroline, sarpagine and ajmaline-related indole alkaloids

Cited by 89 publications

References 94 publications

General Strategy for Synthesis of C-19 Methyl-Substituted Sarpagine/Macroline/Ajmaline Indole Alkaloids Including Total Synthesis of 19(S),20(R)-Dihydroperaksine, 19(S),20(R)-Dihydroperaksine-17-al, and Peraksine

General Strategy for Synthesis of C-19 Methyl-Substituted Sarpagine/Macroline/Ajmaline Indole Alkaloids Including Total Synthesis of 19(S),20(R)-Dihydroperaksine, 19(S),20(R)-Dihydroperaksine-17-al, and Peraksine

Transition Metal‐Catalyzed Synthesis of Fused Five‐Membered Aromatic Heterocycles

Biology‐Oriented Combined Solid‐ and Solution‐Phase Synthesis of a Macroline‐Like Compound Collection

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