“Cut and Sew” Transformations via Transition-Metal-Catalyzed Carbon–Carbon Bond Activation

Abstract

The transition metal-catalyzed “cut and sew” transformation has recently emerged as a useful strategy for preparing complex molecular structures. After oxidative addition of a transition metal into a carbon–carbon bond, the resulting two carbon termini can be both functionalized in one step via the following migratory insertion and reductive elimination with unsaturated units, such as alkenes, alkynes, allenes, CO and polar multiple bonds. Three- or four-membered rings are often employed as reaction partners due to their high ring strains. The participation of non-strained structures generally relies on cleavage of a polar carbon–CN bond or assistance of a directing group.

Theoretical Study of Rhodium‐Catalyzed C−C Activation of Cyclobutanones: Origin of Ligand‐Controlled Product Selectivity

“…In particular, cyclobutanone subunits play a prominent role in organic chemistry because they can be easily obtained from olefins and are highly reactive in C−C activation. Ring‐opening reactions of cyclobutanone derivatives and subsequent insertion of π‐unsaturated units give efficient access to enhanced molecular complexity in organic syntheses …”

“…Ring-opening reactions of cyclobutanone derivatives and subsequent insertion of π-unsaturated units give efficient access to enhanced molecular complexity in organic syntheses. [4] Cyclobutanone CÀ C activation with a Rh(I) catalyst has great potential for the synthesis of fused- [5] and bridged-ring [6] systems. However, this synthetic application is greatly limited because of direct CO extrusion from cyclobutanone, which leads to formation of cyclopropane as a byproduct.…”

Cobalt‐Catalyzed Reductive Dimethylcyclopropanation of 1,3‐Dienes

“…[6] The Simmons–Smith reaction is potentially well-suited to addressing these structures; however, it is known that the efficiency of Zn carbenoid-based cyclopropanations decreases significantly when using disubstituted gem -dihaloalkanes. [7] For example, the addition of 2,2-diiodopropane under Furukawa conditions has only been demonstrated for two simple substrates, cyclopentene and cyclohexene, which provide yields up to 59% after a reaction time of 5 days.…”

Rhodium(I)‐Catalyzed Ring‐Closing Reaction of Allene–Alkene–Alkynes: One‐Step Construction of Tricyclo[6.4.0.02,6] and Bicyclo[6.3.0] Skeletons from Linear Carbon Chains

“…YasuakiK awaguchi, Asami Nagata, Kei Kurokawa, Haruna Yokosawa, and ChisatoM ukai* [a] Abstract: Treatment of dodecatrienyne derivatives with [RhCl(CO) 2 ] 2 in refluxing toluenee ffected the cycloisomerization to produce tricyclo[6.4.0.0 2,6 ]dodecadienes. The one-carbon shortened undecatrienyne derivatives, however,a fforded bicyclo[6.3.0]undecatriene derivatives instead of tricyclicc ompounds, the latter of which are well known as ab asic skeleton of naturallyo ccurring octanoids.O n the basis of two experimentsw ith deuteratedsubstrates, ap lausible reaction mechanism for the constructiono f these productsw as proposed.…”