English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Platinum- and Acid-Catalyzed Enyne Metathesis Reactions:  Mechanistic Studies and Applications to the Syntheses of Streptorubin B and Metacycloprodigiosin

Fürstner, A., Szillat, H., Gabor, B., & Mynott, R. (1998). Platinum- and Acid-Catalyzed Enyne Metathesis Reactions:  Mechanistic Studies and Applications to the Syntheses of Streptorubin B and Metacycloprodigiosin. Journal of the American Chemical Society, 120(33), 8305-8314. doi:10.1021/ja981183g.

Item is

Files

show Files
hide Files
:
ja8305.pdf (Supplementary material), 2MB
Name:
ja8305.pdf
Description:
Supporting Information
Visibility:
Public
MIME-Type / Checksum:
application/pdf / [MD5]
Technical Metadata:
Copyright Date:
-
Copyright Info:
-
License:
-
:
ja8305a.pdf (Supplementary material), 769KB
Name:
ja8305a.pdf
Description:
Supporting Information
Visibility:
Public
MIME-Type / Checksum:
application/pdf / [MD5]
Technical Metadata:
Copyright Date:
-
Copyright Info:
-
License:
-
:
ja981183g_s.pdf (Supplementary material), 2MB
Name:
ja981183g_s.pdf
Description:
Supporting Information
Visibility:
Public
MIME-Type / Checksum:
application/pdf / [MD5]
Technical Metadata:
Copyright Date:
-
Copyright Info:
-
License:
-
:
ja981183g_sa.pdf (Supplementary material), 808KB
Name:
ja981183g_sa.pdf
Description:
Supporting Information
Visibility:
Public
MIME-Type / Checksum:
application/pdf / [MD5]
Technical Metadata:
Copyright Date:
-
Copyright Info:
-
License:
-

Locators

show

Creators

show
hide
 Creators:
Fürstner, Alois1, Author              
Szillat, Hauke1, Author              
Gabor, Barbara2, Author              
Mynott, Richard2, Author              
Affiliations:
1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              
2Service Department Mynott (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445627              

Content

show
hide
Free keywords: -
 Abstract: Formal total syntheses of the antibiotics metacycloprodigiosin (2) and streptorubin B (3) are described, which are known to exhibit promising immunomodulating properties. The key step en route to their meta-bridged pyrrole core structures 5 and 7, respectively, consists of a metathesis reaction of electron-deficient enynes catalyzed by either platinum halides, hard Lewis acids, or HBF4. This transformation expands the pre-existing cycloalkene of the substrates by two C atoms, forges the bicyclic pyrrolophane structure of the targets, and simultaneously forms a bridgehead alkene function. The products of this skeletal rearrangement are converted into the targets by a sequence comprising (i) a stepwise reduction of their enone entity to the corresponding saturated alcohols and (ii) an aromatization of the N-tosylated dihydropyrroles 20 and 34 thus obtained via elimination of potassium sulfinate on exposure to KAPA (potassium 3-aminopropylamide). A careful analysis of the minor byproducts formed in the enyne metathesis reactions allows a mechanistic rationale to be proposed for this operationally trivial yet highly attractive transformation which involves “nonclassical” cyclopropylmethyl−homoallyl−cyclobutyl cations as key intermediates. This cationic pathway is distinctly different from mechanistic interpretations of other enyne metathesis reactions previously reported in the literature.

Details

show
hide
Language(s): eng - English
 Dates: 1998-04-081998-08-071998-08-26
 Publication Status: Published in print
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ja981183g
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: American Chemical Society
Pages: 10 Volume / Issue: 120 (33) Sequence Number: - Start / End Page: 8305 - 8314 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870