A concise route to 3‐aryl‐1‐trifluoromethyltetrahydroisoquinolines by a benzylic [1,5]‐hydride shift‐mediated CH bond functionalization was developed. The [1,5]‐hydride shift of the benzylic C(sp3)H bond to the trifluoromethylketimine derived from para‐anisidine occurred smoothly to produce cis‐1‐trifluoromethyl‐3‐aryltetrahydroisoquinolines in good to excellent chemical yields with good diastereoselectivities. In contrast, use of the NH ketimine furnished N‐unprotected tetrahydroisoquinolines in good yields in favor of the trans‐isomer.magnified image

Highly diastereoselective synthesis of tricyclic fused-pyrans was achieved by Brønsted acid catalyzed double C(sp3)–H bond functionalization.

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Synthesis of 3-Aryl-1-trifluoromethyltetrahydroisoquinolines by Broensted Acid-Catalyzed C(sp 3 )-H Bond Functionalization. -The Tf2NH-catalyzed title cyclization proceeds diastereoselectively in favour of cis isomers for N-protected imines (I) and (IV) and trans isomers for unprotected imines (IX). -(MORI, K.; UMEHARA, N.; AKIYAMA*, T.; Adv. Synth. Catal. 357 (2015) 5, 901-906, http://dx.doi.org/10.1002/adsc.201400775 ; Dep. Chem., Fac. Sci., Gakushuin Univ., Toshima, Tokyo 171, Japan; Eng.) -M. Tismer 30-208