1986
DOI: 10.1002/ange.19860980817
|View full text |Cite
|
Sign up to set email alerts
|

Dihydroacepentalendiid, das Dianion des Acepentalens

Abstract: Dihydroacepentalendiid 22e, formal ein ethenoiiberbriicktes Dihydropentalendiid''], sollte wie dieses['**] nach semiempirischen Rechnungen ein geschlossenschaliges System seini31. Allerdings diirfte seiner Bildung die hohe Spannungsenergie in dem cyclisch und gekreuzt konjugierten Geriist rnit drei angular anellierten Flinfringenf4I entgegenstehen. Bisher war es offenbar nicht gelungen, 22e zu erzeugen, obwohl sich die Theoretiker schon lange fur Acepentalen (Cyclopenta[cd]pentalen) 2 interessiered". Neueste V… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
1
1
1

Citation Types

0
3
0

Year Published

1989
1989
2016
2016

Publication Types

Select...
5
2
1

Relationship

1
7

Authors

Journals

citations
Cited by 21 publications
(3 citation statements)
references
References 14 publications
0
3
0
Order By: Relevance
“…Besides the discussion on the long-assumed homoconjugative interaction between the π bonds of 18 , the generation and properties of the triquinacene-10-yl cation was put forward. ,, Many bridgehead-functionalized derivatives of triquinacene, such as 19 , a few centro -substituted ones, e.g., 20 , , and peripherally functionalized ones, e.g., the interesting all- exo -hexaol 22 , have been described and studied, mainly with respect to their reactivity toward complexation with metal carbonyl fragments, reduction, and elimination. The deprotonation/dehydrogenation pathways of 18 and some derivatives by use of superbases have also been studied in great detail, , and the existence of neutral acepentalene ( 23 ), having remained elusive in condensed media, was demonstrated in the gas phase . More recently, the azatriquinacenes, including the parent, convex/concave heterocentropolyquinane 24 , have attracted some attention because of the particularly exposed basic nitrogen center.
…”
Section: Centropolyquinanesmentioning
confidence: 99%
“…Besides the discussion on the long-assumed homoconjugative interaction between the π bonds of 18 , the generation and properties of the triquinacene-10-yl cation was put forward. ,, Many bridgehead-functionalized derivatives of triquinacene, such as 19 , a few centro -substituted ones, e.g., 20 , , and peripherally functionalized ones, e.g., the interesting all- exo -hexaol 22 , have been described and studied, mainly with respect to their reactivity toward complexation with metal carbonyl fragments, reduction, and elimination. The deprotonation/dehydrogenation pathways of 18 and some derivatives by use of superbases have also been studied in great detail, , and the existence of neutral acepentalene ( 23 ), having remained elusive in condensed media, was demonstrated in the gas phase . More recently, the azatriquinacenes, including the parent, convex/concave heterocentropolyquinane 24 , have attracted some attention because of the particularly exposed basic nitrogen center.
…”
Section: Centropolyquinanesmentioning
confidence: 99%
“…A more versatile approach to 4,7-disubstituted dihydroacepentalenes 65 is via the stable acepentalene dianion 64 as an easily accessible intermediate. Dipotassium acepentalenediide 64 can be obtained in virtually quantitative yield by treatment of triquinacene 10 with the superbasic mixture of potassium t-pentoxide and butyllithium [or even better potassium t-butoxide, butyllithium and tetramethylethylenediamine (TMEDA)] in hexane, the so-called Lochmann-Schlosser base (Scheme 15) [62,63]. Mechanistically this transformation has been shown to proceed via a threefold deprotonation at the three allylic positions in 10 and a subsequent hydride elimination of the central hydrogen from the intermediate trianion to form the dianion as in 64 [64].…”
Section: Potential Acepentalene Precursors and The Elusive Acepentalenementioning
confidence: 99%
“…During the last two decades interest in the study of molecules that contain significant amounts of strain energy in their molecular structure has increased. The questions of bonding character, π overlap, and Hückel stabilization are of great importance to computational and organic chemists. The desire to better understand the bonding character of carbon has prompted the study of the synthesis of a number of strained molecules termed polyquinenes . Dicyclopenta[ a,e ]pentalene ( 1 ) and dicyclopenta[ a,f ]pentalene ( 2 ) (Figure ) have not been synthesized and have been discussed only from a computational point of view.…”
Section: Introductionmentioning
confidence: 99%