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1.2.3.1.1.5 Room-Temperature Reactions

DOI: 10.1055/sos-SD-223-00066

Martin, A. R.Science of Synthesis: N-Heterocyclic Carbenes in Catalytic Organic Synthesis, (20161169.

Several complexes, such as 14 (L = IPr or L = IPr*) and 13 (L = SIPr), are able to promote aryl amination at room temperature.[‌12‌,‌13‌,‌19‌,‌23‌] In addition to these, 11 (L = IPr*OMe), 13 (L = IPr*), and 26 [PdCpCl(SIPr)] also exhibit high reactivity at this temperature.[‌18‌,‌31‌‌33‌] However, a strong base, usually a tert-butoxide or a 2-methylbutan-2-olate salt, is required under these conditions and thus, base-sensitive functional groups are not tolerated. Nevertheless, the coupling between activated or deactivated (het)aryl chlorides and secondary (cyclic) alkylamines or anilines typically proceeds in high yields (82–99%). It is noteworthy that complex 13 (L = IPr*) is also efficient at room temperature, even under solvent-free conditions, particularly when highly encumbered partners are used (Scheme 11).

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