Hypervalent Iodine Oxidation of Allenes: Synthesis of 3-Acetoxy-3-alkoxypropynes, 2-Alkoxy-3-tosyloxypropanals and Phenyl-Substituted Propenals and Propenones

Fluorinative Rearrangements of Substituted Phenylallenes Mediated by (Difluoroiodo)toluene: Synthesis of α‐(Difluoromethyl)styrenes

“…It was subjected to the general reaction conditions,and it underwent fluorinative rearrangement to give b,b-D 2 -adiflurormethyl styrene [D 2 ]-3a in 67 %yield. No indication of deuterium scrambling was observed by either 1 H, 2 Ho r 19 FNMR, thus confirming that the terminal olefin of the allene is not involved in the reaction.…”

“…To our knowledge,t here are only two reports related to the envisioned reaction, and they disclosed widely differing outcomes.M oriarty and co-workers reported that phenylallene was unreactive with PhI(OAc) 2 ,b ut it reacted with Kosersr eagent to give a-formylstyrene (Scheme 1a). [19] Conversely,M uÇiz and co-workers recovered regioisomeric propargyl amines from the oxidative amination reaction between phenylallene and PhI(NTs 2 ) 2 (Scheme 1b). [20] If TolIF 2 were to react chemo-and regioselectively with the internal, conjugated olefin of 2,a nd if the fluorination sequence were to be interrupted by a1 ,2-phenyl shift, a-(difluoromethyl)styrenes would result (Scheme 1c).…”

Fluorinative Rearrangements of Substituted Phenylallenes Mediated by (Difluoroiodo)toluene: Synthesis of α‐(Difluoromethyl)styrenes

“…To our knowledge, there are only two reports related to the envisioned reaction, and they disclosed widely differing outcomes. Moriarty and co‐workers reported that phenylallene was unreactive with PhI(OAc) 2 , but it reacted with Koser's reagent to give α‐formylstyrene (Scheme a) . Conversely, Muñiz and co‐workers recovered regioisomeric propargyl amines from the oxidative amination reaction between phenylallene and PhI(NTs 2 ) 2 (Scheme b) .…”

Chlorination of phenylallene derivatives with 1-chloro-1,2-benziodoxol-3-one: synthesis of vicinal-dichlorides and chlorodienes

“…In contrast, Muñiz reported that with PhI(NTs 2 ) 2 , an oxidative amination occurred via cation B , giving regioisomeric propargylamides upon elimination of the iodanyl adduct (Scheme 1) [37]. Moriarty and Murphy, respectively, showed how reactions of arylallenes with either PhI(OH)OTs [38] or TolIF 2 [39] provide α-disubstituted styrenes by sequences involving intermediates analogous to B , followed by a 1,2-phenyl shift ( C to D , Scheme 1). There has been no investigation of the chemistry between arylallenes and chlorinated hypervalent iodine reagents, and given the differing reactivities that might be achievable with (dichloroiodo)benzene [40] ( 1a ) and chlorobenziodoxolone ( 1b ) [30,41–45], there is potential for the selective generation of diverse, poly-chlorinated scaffolds.…”