molecules Article Markovnikov-Type Hydrotrifluoromethylchalcogenation of Unactivated Terminal Alkenes with [Me4N][XCF3] (X = S, Se) and TfOH Jin Shi and Cheng-Pan Zhang * School of Chemistry, Chemical Engineering and Life Science, Wuhan University of Technology, 205 Luoshi Road, Wuhan 430070, China;
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[email protected]; Tel.: +86-181-086-22150 Academic Editor: Toshifumi Dohi Received: 17 September 2020; Accepted: 30 September 2020; Published: 3 October 2020 Abstract: The first Markovnikov-type hydrotrifluoromethylselenolation of unactivated terminal alkenes with the readily accessible [Me4N][SeCF3] reagent and the superacid TfOH is reported. The reaction proceeded at room temperature under catalyst- and additive-free conditions to give the branched trifluoromethylselenolated products in good yields. This protocol is also applicable to the Markovnikov-type hydrotrifluoromethylthiolation of unactivated terminal alkenes using [Me4N][SCF3]/TfOH, but not to the hydrotrifluoromethoxylation with CsOCF3/TfOH under the same conditions. The successful hydrotrifluoromethylselenolation and hydrotrifluoromethylthiolation showed simplicity and high regioselectivity, taming the sensitive −XCF3 (X = Se, S) anions with TfOH, and offered a convenient method for the straightforward synthesis of branched trifluoromethyl selenoethers and thioethers from unactivated alkenes. Keywords: hydrotrifluoromethylselenolation; hydrotrifluoromethylthiolation; Markovnikov-type; terminal alkene; superacid 1. Introduction