Rhodium(I)‐Catalyzed Intramolecular Carbonylative [2+2+1] Cycloaddition of Bis(allene)s: Bicyclo[6.3.0]undecadienones and Bicyclo[5.3.0]decadienones

Abstract

Ohne Templat: Die Titelreaktion führt leicht und in hohen Ausbeuten zu Bicyclo[6.3.0]undecadienonen (siehe Schema), wobei der Ringschluss auch ohne Templateffekt effizient abläuft. Die vorgestellte Methode kann zum Aufbau von Bicyclo[5.3.0]‐ und Bicyclo[4.3.0]‐Ringsystemen verwendet werden. Ts=p‐Toluolsulfonyl.

A Rh-Catalyzed Cycloisomerization/Diels–Alder Cascade Reaction of 1,5-Bisallenes for the Synthesis of Polycyclic Heterocycles

“…Mukai and coworkers 10 also managed to isolate an exocyclic diene when the initial bisallene was terminal although these bisallenes had the particularity of having two SO2Ph groups at the internal carbon atom of the allene (Scheme 1c). Carbonylative [2+2+1] cycloadditions have been described by the groups of Mukai 10,11 (Scheme 1c) and Chung, 12 although this latter group used cobalt/rhodium heterobimetallic nanoparticles. In both cases, the authors postulated that the external double bonds of both allenes were involved in the oxidative cyclization step, affording a seven-membered scaffold.…”

“…Therefore, developing cycloaddition reactions of bisallenes with a third unsaturation being able to control the formation of a seven-membered ring is highly desirable. To the best of our knowledge, the Pauson-Khand-type reaction developed by Mukai 11 is the only example of such a process reported to date. Given these precedents, and based on our previous experience with Rh-catalyzed cycloaddition reactions involving allenes, 14 we envisaged developing a cycloaddition reaction between 1,5bisallenes and alkenes with the aim of controlling the reaction towards the synthesis of fused seven-six-membered bicyclic systems.…”

Rhodium(I)‐Catalyzed Intramolecular Carbonylative [2+2+1] Cycloadditions and Cycloisomerizations of Bis(sulfonylallene)s

“…Characterization data for the products are given in the Supporting Information of ref. [14]. [{RhCl(CO)dppp} 2 ] (4.9 mg, 4.2 10 À3 mmol) was added to a solution of 23 a (23.0 mg, 4.22 10 À2 mmol) in xylene (1.0 mL).…”

“…This paper describes the Rh I -catalyzed carbonylative and non-carbonylative ring-closing reactions of bis(sulfonyl-A C H T U N G T R E N N U N G allene)s to effect the easy preparation of medium-sized bicycloA C H T U N G T R E N N U N G [n.3.0] skeletons and monocyclic rings containing two vicinal exo-methylene moieties, respectively. [14] Results and Discussion G none systems could not be achieved except in the cases of a few specific substrates, possessing, for example, an aromatic ring as the template. [15] [16] of allenynes (alkyne/allene derivatives) [13,17,18] or allenenes (al-A C H T U N G T R E N N U N G kene/allene) [7] has, however, been reported, by ourselves [7,13] and by Brummond et al, [17] to afford the corresponding biA C H T U N G T R E N N U N G cy- 3.0] compounds in satisfactory yields.…”

Rhodium(I)‐Catalyzed Intramolecular [5+2] Cycloaddition Reactions of Alkynes and Allenylcyclopropanes: Construction of Bicyclo[5.4.0]undecatrienes and Bicyclo[5.5.0]dodecatrienes

“…Our continuing interest in the field of the [{RhCl(CO) 2 } 2 ]and [{RhCl(CO)dppp} 2 ]-catalyzed cycloaddition reactions of phenylsulfonylallenes [7] prompted us to investigate the intramolecular cycloaddition reaction between phenylsulfonylallenes that contain a cyclopropyl group at the allene terminus and alkynes. Herein, we describe the preliminary results of the Rh I -catalyzed ring-closing reaction of alkyne-allenylcyclopropane derivatives for the facile preparation of the bicyclo [5.4.0]undecatrienes and bicyclo [5.5.0]dodecatrienes.…”