We describe here the facile construction of sterically hindered tertiary alkyl ethers and thioethers via the Zn(OTf)-catalyzed coupling of alcohols/phenols with unactivated tertiary alkyl bromides and the Cu(OTf)-catalyzed thiolation of unactivated tertiary alkyl oxalates with thiols. The present protocol represents one of the most effective unactivated tertiary C(sp)-heteroatom bond-forming conditions via readily accessible Lewis acid catalysis that is surprisingly less developed.
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