Diin‐Reaktion, XXXV¹⁾ Reaktionen von Rhodiumkomplexen mit Cycloalkinen und mit Dehydrobenzol

Abstract

Die Reaktivitat der Rhodiumkomplexe 1-3 von o-Diketo-diin-Derivaten gegeniiber gespannten cyclischen Acetylenen wird untersucht. Die Tetra-, Penta-, Hexa-und Oktamethylen-1,2,3selenadiazole 4, die als Vorstufen fur die cyclischen Acetylene dienen, sowie die stabilen 8-und logliedrigen Cycloalkine 9 reagieren mit den Rhodiumkomplexen 1-3 unter Bildung von substituierten Chinon-Derivaten 5. Dagegen bildet sich bei der Umsetzung der Komplexe 1-3 mit Cyclopenteno-1,2,3-selenadiazol (4e) das 1 ,CDiselenin 8. -Mit Dehydrobenzol setzen sich die Rhodiumkornplexe nicht urn. Diyne Reaction, XXXVI). -Reactions of Rhodium Complexes with Cycloalkynes andThe reactivity of the rhodium complexes 1-3 of o-diketo diyne derivatives towards strained cyclic acetylenes is examined. The tetra-, penta-, hexa-, and octarnethylene-l,2,3-~elenadiazoles 4, as well as the stable 8-and 10-membered cycloalkynes 9 react with the rhodium complexes 1 -3 to form substituted quinone derivatives 5. The reaction of the complexes 1-3 with cyclopenteno-l,2,3-selenadiazole (4e) leads to 1,4-diselenine 8. -Dehydrobenzene does not react with the rhodium complexes.Die Rhodiumkomplexe 1, 2 und 3, die durch Umsetzung von 1,2-Bis(phenylpropioloyl)benzol, 1,2-Bis(l-oxo-2-butinyl)benzol sowie von 2,3-Bis(l-oxo-2-butinyl)naphthalin mit Tris(triphenylphosphin)rhodium(I)-chlorid erhaltlich sind, reagieren mit den verschiedensten Acetylenderivaten unter Bildung von substituierten Anthraoder Naphthacenchinon-Derivaten 1 -3. Die grol3e Affinitat dieser Komplexe 1-3 gegeniiber Acetylenen und die Variationsmoglichkeit dieser komplexchemischen Chinonsynthesen wurden vor kurzem an Hand von zahlreichen Beispielen aufgezeigt 2). I n der vorliegenden Arbeit wird das Verhalten gespannter Cycloalkin-Derivate ein-schlieRlich instabiler, in Substanz nicht mehr isolierbarer cyclischer Acetylene sowie des Dehydrobenzols gegeniiber den Rhodiumkomplexen 1-3 untersucht.

The Dehydro-Diels−Alder Reaction

“…The first example of a DDA reaction involving a transition metal was reported by Müller in the 1970s. Thus, rhodium complex 127 , obtained from diyne 126 upon treatment with the Wilkinson catalyst Rh(PPh 3 ) 3 Cl, undergoes a reaction to naphthacene 128 under harsh conditions and with low yields (Scheme ) . Naturally, this is not a catalyzed reaction particularly as the direct thermal cyclization from 126 to 128 takes place under milder conditions .…”

Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

“…The results have been collected in a review in 1974 815 and a few later publications. 586,807,816,817 According to Scheme 73, a diyne compound 507 is reacted with, in most cases, Rh-(PPh 3 ) 3 Cl. It is suggested that as the first step toward the isolable rhodacyclopentadiene complexes 509 a rhodacyclopropene complex 508 is formed which is π-coordinated to the triple bond of the second alkyne.…”

“…One of the oldest examples of stoichiometric, metal-assisted syntheses of (fused) benzene derivatives following a [2+2+2] protocol is the “diyne reaction” discovered by Müller. The results have been collected in a review in 1974 and a few later publications. ,,, According to Scheme , a diyne compound 507 is reacted with, in most cases, Rh(PPh 3 ) 3 Cl. It is suggested that as the first step toward the isolable rhodacyclopentadiene complexes 509 a rhodacyclopropene complex 508 is formed which is π-coordinated to the triple bond of the second alkyne.…”

The Photo-Dehydro-Diels-Alder Reaction: An Efficient Route to Naphthalenes

“…The classic examples of the DDA proceed under very drastic conditions. D i e l s -A l d e r r e a c t i o n D e h y d r o -D i e l s -A l d e r r e a c t i o n b ) rhodium 10 and nickel 11 catalysts were used in the DDA. To the best of our knowledge, photochemical excitation was never used to trigger the DDA between acetylenes and arylacetylenic ketones.…”