Intramolecular Pd-catalyzed carboetherification and carboamination. Influence of catalyst structure on reaction mechanism and product stereochemistry

Journal of the American Chemical Society
Josephine S NakhlaJohn P Wolfe

Abstract

The intramolecular Pd-catalyzed carboetherification of alkenes affords 2-indan-1-yltetrahydrofuran products in moderate to good yield with good to excellent levels of diastereoselectivity. The stereochemical outcome of these reactions is dependent on the structure of the Pd catalyst. Use of PCy(3) or P[(4-MeO)C(6)H(4)](3) as the ligand for Pd leads to syn-addition of the arene and the oxygen atom across the double bond, whereas use of (+/-)-BINAP or DPP-benzene affords products that result from anti-addition. The catalyst-induced change in stereochemistry is likely due to a change in reaction mechanism. Evidence is presented that suggests the syn-addition products derive from an unprecedented transannular alkene insertion of an 11-membered Pd(Ar)(OR) complex. In contrast, the anti-addition products appear to arise from Wacker-type anti-oxypalladation. Studies on analogous Pd-catalyzed intramolecular carboamination reactions, which afford 2-indan-1-ylpyrrolidines that result from syn-addition, are also described.

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Citations

Jun 19, 2010·Journal of the American Chemical Society·Asa D MelhadoF Dean Toste
Oct 20, 2011·Journal of the American Chemical Society·Paul B White, Shannon S Stahl
Jun 23, 2012·Journal of the American Chemical Society·Yan MillerSherry R Chemler
Feb 20, 2010·Journal of the American Chemical Society·Baoguo ZhaoYian Shi
Jun 20, 2007·Chemical Society Reviews·Ana Minatti, Kilian Muñiz
Mar 16, 2016·Journal of the American Chemical Society·Gustavo M Borrajo CallejaClément Mazet
Oct 19, 2016·Journal of the American Chemical Society·Scott A ShulerDonald A Watson
Jan 24, 2009·Journal of the American Chemical Society·Sayuri HayashiKoichiro Oshima
Nov 8, 2014·Chemistry : a European Journal·Pavel Kočovský, Jan-E Bäckvall
Jul 24, 2018·Chemistry : a European Journal·Theresa SchitterDaniel B Werz
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Jan 9, 2019·Chemistry : a European Journal·Phillip D G GreenwoodJerome Waser
Oct 12, 2010·Organic & Biomolecular Chemistry·Matthew McConvilleJianliang Xiao
Dec 22, 2009·Organic & Biomolecular Chemistry·Clémence Queffélec, Jean-Luc Montchamp
Feb 24, 2012·Chemical Society Reviews·Zhuangzhi ShiNing Jiao
Jul 9, 2013·Angewandte Chemie·Patrick S Hanley, John F Hartwig
Jul 16, 2020·Chemical Communications : Chem Comm·Akash G TatheNitin T Patil
May 22, 2020·Angewandte Chemie·Mathilde RigouletDidier Bourissou
Nov 14, 2017·Asian Journal of Organic Chemistry·Zachary J GarletsJohn P Wolfe

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