Highly regio- and stereoselective hydrometallation reactions of fluorine-containing internal alkynes: Novel approaches to fluoroalkylated alkenes

Pyrene-based metal–organic framework NU-1000 photocatalysed atom-transfer radical addition for iodoperfluoroalkylation and (Z)-selective perfluoroalkylation of olefins by visible-light irradiation

“…The ratio of (Z)-/(E)-isomers should represent the balance status of 'tugof-war' between iodo and aryl group, and it was interesting to examine the (Z)-/(E)-ratio if iodine atom of 6b was absent, since it might provide a pathway for the facile preparation of (Z)enriched peruoroalkyl styrenes (caution: the (Z)-geometry here refers to the case of aryl moiety) which was of potential interest in pharmaceutical eld and generally needed multi-step synthesis. 79,80 By merging photocatalytic ATRA of R f I onto styrene and subsequent elimination of HI together in one pot, we successfully developed a strategy for the highly stereoselective preparation of (Z)-peruoroalkyl styrene derivatives 7 in moderate to good yields (Scheme 6). To the best of our knowledge, it was the rst time to develop the direct transformation from styrene to (Z)-selective peruoroalkyl styrene.…”

Stereodivergent Hydrosilylation, Hydrostannylation, and Hydrogermylation of α-Trifluoromethylated Alkynes and Their Synthetic Applications

“…1 In particular, the structural editing of natural products with fluorinated motifs can lead to improved biological activities, as exemplified in the epothilone series wherein the C12-C13 trisubstituted epoxide of the natural product was replaced by a (E)-trifluoromethyl-substituted alkene in fludelone, thereby enhancing the therapeutic index of this promising antimitotic compound (Scheme 1). 2 In addition, incorporation of 19 F atoms into natural product derivatives is also a unique strategy to investigate the biological mechanisms that the latter induce by multinuclear NMR owing to the magnetic properties of the fluorine atom. 3 Representative examples of such a fascinating endeavor have been reported in fluorinated probes 1, 2, and 3 derived from amphotericin, 4 parthenolide, 5 or bafilomycin, respectively (Scheme 1).…”

“…18 Hydro-and carbocupration of 9 were also developed by the same group and excellent regio-and stereoselectivities were noticed. 19 However, only potent electrophiles could be used to trap the intermediate vinylcopper species 13 (Scheme 3, eq. 3).…”

“…4). 19 Rare examples of hydrostannylation reactions of α-CF 3alkynes have been reported since the seminal work of Cullen and Styan in 1966, 20,21…”

One-Pot Multistep Synthesis of Trisubstituted Alkenes from N-Tosylhydrazones and Alcohols

“…19, 142.40, 137.75, 136.76, 129.82, 128.77, 128.37, 127.37, 127.14, 126.89, 126.76, 125.51, 23.25, 20.11, 13.49. (3,3,3-Trifluoroprop-1-ene-1,2-diyl) 1-Methyl-4-(3,3,3-trifluoro-2-phenylprop-1-enyl)benzene (4b) 23 Colorless liquid; yield (Z/E): 95.6 mg (73%); ratio Z/E 11:89 ( 1 H NMR); R f = 0.66 (PE). 1-Bromo-2-(3,3,3-trifluoro-2-phenylprop-1-enyl) Bromo-4-(3,3,3-trifluoro-2-phenylprop-1-enyl) 2-(3,3,3-Trifluoro-2-phenylprop-1-enyl) Bromo-2-(3,3,3-trifluoro-1-phenylprop-1-en-2-yl) Bromo-3-(3,3,3-trifluoro-1-phenylprop-1-en-2-yl) 1-Bromo-4-(3,3,3-trifluoro-1-phenylprop-1-en-2-yl) Methyl-4-(3,3,3-trifluoro-1-phenylprop-1-en-2-yl)…”