A hypervalent iodine reagent-based α-carbonyl dihalogenation reaction is reported. Treating diazoacetate derivatives with either iodobenzene dichloride or iodotoluene difluoride results in gem-dichlorination or gem-difluorination products, respectively. The reaction is catalyzed by either Lewis acid or Lewis base activation of the aryl-λ(3)-iodane (ArIX2) species and proceeds rapidly and chemoselectively to the desired gem-difunctionalized products in good to excellent yield.
New high-resolution visible Fourier transform emission spectra of the A (2)Π → X (2)Σ(+) and B' (2)Σ(+) → X (2)Σ(+) systems of (24)MgD and of the B' (2)Σ(+) → X (2)Σ(+) systems of (25,26)MgD and (25,26)MgH have been combined with earlier results for (24)MgH in a multi-isotopologue direct-potential-fit analysis to yield improved analytic potential energy and Born-Oppenheimer breakdown functions for the ground X (2)Σ(+) state of MgH. Vibrational levels of the ground state of (24)MgD were observed up to v" = 15, which is bound by only 30.6 ± 0.10 cm(-1). Including deuteride and minor magnesium isotopologue data allowed us also to determine the adiabatic Born-Oppenheimer breakdown effects in this molecule. The fitting procedure used the recently developed Morse/Long-Range (MLR) potential energy function, whose asymptotic behavior incorporates the correct inverse-power form. A spin-splitting radial correction function to take account of the (2)Σ spin-rotation interaction was also determined. Our refined value for the ground-state dissociation energy of the dominant isotopologue ((24)MgH) is D(e) = 11,104.25 ± 0.8 cm (-1), in which the uncertainty also accounts for the model dependence of the fitted D(e) values for a range of physically acceptable fits. We were also able to determine the marked difference in the well depths of (24)MgH and (24)MgD (with the deuteride potential curve being 7.58 ± 0.30 cm(-1) deeper than that of the hydride) as well as smaller well-depth differences for the minor (25,26)Mg isotopologues. This analytic potential function also predicts that the highest bound level of (24)MgD is v" = 16 and that it is bound by only 2.73 ± 0.10 cm(-1).
A combined experimental and computational investigation was conducted to identify a mild and effective Lewis‐acidic activator for TolIF2 in the gem‐difluorination of diazo compounds. Computationally, borosilicate, a common constituent of laboratory glassware, was found to spontaneously activate TolIF2, and an extensive experimental survey confirmed borosilicate as the most effective activator to date. The key to realizing this borosilicate‐activated reaction was the use of high purity TolIF2, which is prepared by a reproducible, multigram‐scale synthesis.
A rapid, mild and metal-free intermolecular cyclopropanation between iodonium ylides and alkene-containing substrates mediated by PhI(OAc)·BuNI is reported. Iodonium ylides of cyclic and acyclic 1,3-dicarbonyls were reacted with a variety of mono-, di-, tri- and tetra-substituted alkenes of various structural types to give 29 cyclopropanes in up to 97% yield.
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