1222085-72-4Relevant academic research and scientific papers
Breaking conjugation: Unusual regioselectivity with 2-substituted allylic substrates in the Tsuji-Trost reaction
Kim, Byeong-Seon,Hussain, Mahmud M.,Norrby, Per-Ola,Walsh, Patrick J.
, p. 1241 - 1250 (2014/03/21)
η3-Allyl palladium complexes are key intermediates in Tsuji-Trost allylic substitution reactions. It is well known that (η3-1-aryl-3-alkyl substituted allyl)Pd intermediates result in nucleophilic attack at the alkyl substituted terminus. In contrast, the chemistry of (η3-1,2,3-trisubstituted allyl)Pd intermediates is relatively unexplored. Herein we probe the regioselectivity with 1,2,3-trisubstituted allylic substrates in Tsuji-Trost allylic substitution reactions. DFT investigation of cationic (η3-1-Ph-2-B(pin)-3- alkyl-allyl)Pd(PPh3)2 intermediates predict that nucleophilic attack should occur preferentially on anti-allyls rather than the syn-isomers to generate benzylic substitution products under Curtin-Hammett conditions. Experimentally, systematic studies with 1,2,3-trisubstituted allylic substrates revealed that a Linear Free Energy Relationship (LFER) is observed when Charton steric parameters of the C-2 substituents are plotted against the log of the ratio of regioisomers. Bulkier C-2 substituents in 1,2,3-trisubstituted η3-allyl palladium intermediates provide stronger preference for nucleophilic attack at anti-oriented benzylic termini. Additionally, the geometry of 1,4-elimination products supports the presence of anti-allyl palladium intermediates. The Royal Society of Chemistry 2014.
Allylie substitution versus Suzuki cross-coupling: Capitalizing on chemoselectivity with bifunctional substrates
Hussain, Mahmud M.,Walsh, Patrick J.
supporting information; experimental part, p. 1834 - 1837 (2010/06/21)
One catalyst, two reactions-a tale of chemoselectivity: Given the choice between an allylic acetate and a vinylboronate ester, palladium preferentially reacts with the allylic acetate to give the allylic substitution product. In the presence of an aryl bromide and base, Suzuki cross-coupling subsequently ensues to afford allylic amines (see scheme; pin = pinacol, THF = tetrahydrofuran). Chemical equation representation
