Deconvoluting the memory effect in Pd-catalyzed allylic alkylation: Effect of leaving group and added chloride

Chemistry : a European Journal
Peter FristrupPer-Ola Norrby

Abstract

An analysis of product distributions in the Tsuji-Trost reaction indicates that several instances of reported "memory effects" can be attributed to slow interconversion of the initially formed syn- and anti-[Pd(eta3-allyl)] complexes. Addition of chloride triggers a true memory effect, in which the allylic terminus originally bearing the leaving group has a higher reactivity. The latter effect, termed regioretention, can be rationalized by ionization from a palladium complex bearing a chloride ion, forming an unsymmetrically substituted [Pd(eta3-allyl)] complex. DFT calculations verify that the position trans to the phosphine ligand is more reactive both in the initial ionization and in the subsequent nucleophilic attack.

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Citations

Oct 30, 2007·Beilstein Journal of Organic Chemistry·Dominik A Lange, Bernd Goldfuss
Feb 20, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Ryan W Carlsen, Daniel H Ess
Oct 23, 2015·Angewandte Chemie·Peter VertesaljaiAlexander J Grenning
Nov 16, 2007·Chemistry : a European Journal·Uli KazmaierFranz L Zumpe
Sep 20, 2008·Chemical Communications : Chem Comm·Shufeng Chen, Jianbo Wang
Apr 4, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·I Guerrero-Ríos, E Martin
Jan 11, 2008·Organic Letters·Sankar Basak, Uli Kazmaier
May 7, 2015·Journal of the American Chemical Society·Whitney K WalkerDavid J Michaelis
Nov 4, 2006·The Journal of Organic Chemistry·Katja Krämer, Uli Kazmaier
Sep 28, 2006·Journal of the American Chemical Society·Mårten AhlquistPer-Ola Norrby

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