The rhodium-catalyzed, highly N(2) - and N(1) -selective coupling of benzotriazoles with allenes is reported. The exceptionally high N(2) and N(1) selectivities were achieved by using a rhodium(I)/DPEphos and rhodium(I)/JoSPOphos catalyst, respectively. This method permits the atom-economic synthesis of valuable branched N(2) - and N(1) -allylated benzotriazole derivatives and allows for preliminary studies of their reactivity.

New Rh‐ and Pd‐catalyzed regiodivergent and stereoselective intermolecular coupling reactions of imidazole derivatives with mono‐substituted allenes are herein reported. Using a RhI/Josiphos system, perfect regioselectivities and high enantiomeric excess were obtained, while a PdII/dppf system gave linear products with high regioselectivities and high E/Z selectivities. This method permits the atom economic synthesis of valuable branched and linear allylic imidazole derivatives.

The rhodium-catalyzed atom-economic asymmetric N-selective intermolecular addition of purine derivatives to terminal allenes is reported. Branched allylic purines were obtained in high yields, regioselectivity and outstanding enantioselectivity utilizing a Rh/Josiphos catalyst. Conversely, linear selective allylation of purines could be realized in good to excellent regio- and E/Z-selectivity with a Pd/dppf catalyst system. Furthermore, the new methodology was applied to a straightforward asymmetric synthesis of carbocyclic nucleoside abacavir.

New Rh- and Pd-catalyzed regiodivergent and stereoselective intermolecular coupling reactions of imidazole derivatives with mono-substituted allenes are herein reported. Using a Rh(I)/Josiphos system, perfect regioselectivities and high enantiomeric excess were obtained, while a Pd(II)/dppf system gave linear products with high regioselectivities and high E/Z selectivities. This method permits the atom economic synthesis of valuable branched and linear allylic imidazole derivatives.

The rhodium-catalyzed, highly N 2 -and N 1 -selective coupling of benzotriazoles with allenes is reported. The exceptionally high N 2 and N 1 selectivities were achieved by using a rhodium(I)/DPEphos and rhodium(I)/JoSPOphos catalyst, respectively. This method permits the atom-economic synthesis of valuable branched N 2 -and N 1 -allylated benzotriazole derivatives and allows for preliminary studies of their reactivity.