Rapid, Modular, Sterodivergent and Catalytic Construction of Contiguous Elements in Acyclic Series from Alkynes

David Pierrot pdavid@technion.ac.il Jeffrey Bruffaerts Ilan Marek
Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa, Israel

Previous studies in our group showed that strained rings could be easily functionalized and ring-opened to access acyclic molecular frameworks bearing stereocontrolled quaternary centers.1 Following those pioneering works and inspired by the concept of metal-walk,2 we investigated the behaviour of 2-vinylcyclopropylmethanol derivatives in Heck reactions (Scheme 1). We are pleased to report a highly modular and diastereoselective approach that enabled the access to most stereoisomers, in only three catalytic steps from easily accessible starting materials.3

Scheme 1: Rapid and modular access to complex acyclic systemsScheme 1: Rapid and modular access to complex acyclic systems

References:

1. a) S. Singh, J. Bruffaerts, A. Vasseur, I. Marek, Nat. Commun. 2017, 8, 14200; b) S. Raha Roy, D. Didier, I. Marek, Chem. Sci. 2016, 7, 5989; c) F.-G. Zhang, G. Eppe, I. Marek, Angew. Chem. Int. Ed. 2016, 55, 714; d) A. Vasseur, L. Perrin, O. Eisenstein, I. Marek, Chem. Sci. 2015, 6, 2770; e) A. Masarwa, D. Didier, T. Zabrodsky, M. Schinkel, L. Ackermann, I. Marek, Nature 2014, 505, 199.

2. a) A. Vasseur, J. Bruffaerts, I. Marek, Nature Chem. 2016, 8, 209 ; b) T.-S. Mei, H. H. Patel, M. S. Sigman, Nature 2014, 508, 340.

3. D. Didier, P.-O. Delaye, M. Simaan, B. Island, G. Eppe, H. Eijsberg, A. Kleiner, P. Knochel, I. Marek, Chem. Eur. J. 2014, 20, 1038.









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