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Gold C–N/C–O coupling without extra oxidants
Cyclometalated gold catalyzes aryl C–N and C–O coupling in air/water by Au(I)/Au(III) oxidative addition, without sacrificial I(III) or F+ oxidants.
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What is new about these gold C–N couplings?
They proceed without sacrificial oxidants, unlike typical Au(I)/Au(III) catalysis that needs I(III) or F+.
Source: Au(iii)-aryl intermediates in oxidant-free C-N and C-O cross-coupling catalysis · DOI · quote verified
What C–O scope was extended?
From phenols to aliphatic alcohols and water.
Source: Au(iii)-aryl intermediates in oxidant-free C-N and C-O cross-coupling catalysis · DOI · quote verified
Are air and water tolerated?
Yes: absolute tolerance for both air and water is claimed.
Source: Au(iii)-aryl intermediates in oxidant-free C-N and C-O cross-coupling catalysis · DOI · quote verified
What property of the nucleophile governs reactivity?
Its acidity.
Source: Au(iii)-aryl intermediates in oxidant-free C-N and C-O cross-coupling catalysis · DOI · quote verified
What yields did 2-propoxide and t-butoxide give?
21% and 4%, respectively.
Source: Au(iii)-aryl intermediates in oxidant-free C-N and C-O cross-coupling catalysis · DOI · quote verified
What happened with NaOH versus the phenol product?
Phenol 1af only 34%; diaryl ether 1ag was 26% because the phenol, once formed, outcompetes hydroxide.
Source: Au(iii)-aryl intermediates in oxidant-free C-N and C-O cross-coupling catalysis · DOI · quote verified
How did switching NaOH to NaOMe change phenol yield?
Phenol 1af increased up to 52%.
Source: Au(iii)-aryl intermediates in oxidant-free C-N and C-O cross-coupling catalysis · DOI · quote verified
What C–N yield was reached after 48 h for 1ac?
Up to 78% (from 56%).
Source: Au(iii)-aryl intermediates in oxidant-free C-N and C-O cross-coupling catalysis · DOI · quote verified
Which aniline was chosen first and why?
p-Nitroaniline, more acidic (pKa = 20.9 in DMSO).
Source: Au(iii)-aryl intermediates in oxidant-free C-N and C-O cross-coupling catalysis · DOI · quote verified
What solvent/base combo gave 39% early C–N hit?
DMSO with KOt-Bu.
Source: Au(iii)-aryl intermediates in oxidant-free C-N and C-O cross-coupling catalysis · DOI · quote verified
Were Au(III) intermediates isolated?
Yes: novel neutral and cationic C–N cyclometalated Au(III) species were synthesized.
Source: Au(iii)-aryl intermediates in oxidant-free C-N and C-O cross-coupling catalysis · DOI · quote verified