Strereo- and chemoselective hydroformylation of functional olefins using catalysts with secondary coordination sphere

Small-molecule catalysts, equipped with a supplementary coordination sphere, have already proved themselves highly efficient in many important chemical transformations. It was previously demonstrated that attractive interactions between the secondary coordination environment and the substrate largely govern stereoselectivity and the reactivity of the primary catalytic site. This approach may become truly practical if divergent synthesis of libraries of such multifunctional catalysts is available, thus allowing facile shuffling of functional groups in the primary and secondary coordination spheres.

We now wish to demonstrate that the modular 3-D ligands developed by our group^1-3 may serve as a universal platform to examine catalytic reactions guided by secondary coordination sphere-substrate attractive interactions. We now report the results of our investigation on a series of bifunctional PC(sp³)P complexes equipped with different outer-sphere auxiliaries, that allowed stereo- and chemoselective hydroformylation of functionalyzed olefins.

Figure 1.

1. Musa, S.; Shaposhnikov, I.; Cohen, S.; Gelman, D., Angew. Chem., Int. Ed. 2011, 50, 3533.
2. Musa, S.; Ghosh, A.; Vaccaro, L.; Ackermann, L.; Gelman, D., Adv. Synth. Catal. 2015, 357, 2351.
3. Cohen, S.; Borin, V.; Schapiro, I.; Musa, S.; De-Button, S.; Belkova, N.V. and Gelman, D. ACS Catal. 2017, 7, 8139.