Biomimetically Inspired, One-Step Synthesis of Exotine A and Exotine B
The one-step syntheses of exotine A and exotine B, which comprise the unusual coumarin-cyclohepta[b]indole ring system, have been achieved via the biomimetically inspired combination of indole, prenal, and either trans-dehydroosthol or gleinadiene. This facile three-component reaction delivered a mixture (17:1) of exotine A and 11'-epi-exotine A in a 43% yield from trans-dehydroosthol and a mixture (4:1) of exotine B and 11'-epi-exotine B in a 50% yield from gleinadiene. Some mechanistic aspects of this process were explored, and spectral evidence for 3,3'-spiroindolenine intermediates was obtained. Moreover, a skeletal isomer of exotine A that likely originates from a 1,2-alkyl rearrangement of a protonated 3,3'-spiroindolenine was isolated and characterized by X-ray crystallography. These findings not only provide experimental support for Jiang's proposed biosynthesis of exotine A and exotine B but also foreshadow the existence of other exotine-derived natural products having isomeric frameworks. Exploratory attempts to induce an enantioselective 3CR using a chiral phosphoric acid were unsuccessful.
| Medienart: |
E-Artikel |
|---|
| Erscheinungsjahr: |
2021 |
|---|---|
| Erschienen: |
2021 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:86 |
|---|---|
| Enthalten in: |
The Journal of organic chemistry - 86(2021), 16 vom: 20. Aug., Seite 10946-10953 |
| Sprache: |
Englisch |
|---|
| Beteiligte Personen: |
Lepovitz, Lance T [VerfasserIn] |
|---|
| Links: |
|---|
| Themen: |
Coumarins |
|---|
| Anmerkungen: |
Date Completed 21.10.2021 Date Revised 21.10.2021 published: Print-Electronic Citation Status MEDLINE |
|---|
| doi: |
10.1021/acs.joc.0c01524 |
|---|
| funding: |
|
|---|---|
| Förderinstitution / Projekttitel: |
|
| PPN (Katalog-ID): |
NLM314965793 |
|---|
| LEADER | 01000naa a22002652 4500 | ||
|---|---|---|---|
| 001 | NLM314965793 | ||
| 003 | DE-627 | ||
| 005 | 20231225153900.0 | ||
| 007 | cr uuu---uuuuu | ||
| 008 | 231225s2021 xx |||||o 00| ||eng c | ||
| 024 | 7 | |a 10.1021/acs.joc.0c01524 |2 doi | |
| 028 | 5 | 2 | |a pubmed24n1049.xml |
| 035 | |a (DE-627)NLM314965793 | ||
| 035 | |a (NLM)32924509 | ||
| 040 | |a DE-627 |b ger |c DE-627 |e rakwb | ||
| 041 | |a eng | ||
| 100 | 1 | |a Lepovitz, Lance T |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Biomimetically Inspired, One-Step Synthesis of Exotine A and Exotine B |
| 264 | 1 | |c 2021 | |
| 336 | |a Text |b txt |2 rdacontent | ||
| 337 | |a ƒaComputermedien |b c |2 rdamedia | ||
| 338 | |a ƒa Online-Ressource |b cr |2 rdacarrier | ||
| 500 | |a Date Completed 21.10.2021 | ||
| 500 | |a Date Revised 21.10.2021 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a The one-step syntheses of exotine A and exotine B, which comprise the unusual coumarin-cyclohepta[b]indole ring system, have been achieved via the biomimetically inspired combination of indole, prenal, and either trans-dehydroosthol or gleinadiene. This facile three-component reaction delivered a mixture (17:1) of exotine A and 11'-epi-exotine A in a 43% yield from trans-dehydroosthol and a mixture (4:1) of exotine B and 11'-epi-exotine B in a 50% yield from gleinadiene. Some mechanistic aspects of this process were explored, and spectral evidence for 3,3'-spiroindolenine intermediates was obtained. Moreover, a skeletal isomer of exotine A that likely originates from a 1,2-alkyl rearrangement of a protonated 3,3'-spiroindolenine was isolated and characterized by X-ray crystallography. These findings not only provide experimental support for Jiang's proposed biosynthesis of exotine A and exotine B but also foreshadow the existence of other exotine-derived natural products having isomeric frameworks. Exploratory attempts to induce an enantioselective 3CR using a chiral phosphoric acid were unsuccessful | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, N.I.H., Extramural | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 7 | |a Coumarins |2 NLM | |
| 650 | 7 | |a Indoles |2 NLM | |
| 650 | 7 | |a exotine A |2 NLM | |
| 650 | 7 | |a exotine B |2 NLM | |
| 700 | 1 | |a Martin, Stephen F |e verfasserin |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t The Journal of organic chemistry |d 1945 |g 86(2021), 16 vom: 20. Aug., Seite 10946-10953 |w (DE-627)NLM000006343 |x 1520-6904 |7 nnns |
| 773 | 1 | 8 | |g volume:86 |g year:2021 |g number:16 |g day:20 |g month:08 |g pages:10946-10953 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1021/acs.joc.0c01524 |3 Volltext |
| 912 | |a GBV_USEFLAG_A | ||
| 912 | |a GBV_NLM | ||
| 951 | |a AR | ||
| 952 | |d 86 |j 2021 |e 16 |b 20 |c 08 |h 10946-10953 | ||