Direct Introduction of a Dimesitylboryl Group Using Base‐Mediated Substitution of Aryl Halides with Silyldimesitylborane

The first dimesitylboryl substitution of aryl halides with a silylborane bearing a dimesitylboryl group in the presence of alkali‐metal alkoxides is described. The reactions of aryl bromides or iodides with Ph₂MeSi?BMes₂ and Na(OtBu) afforded the desired aryl dimesitylboranes in good to high yields and with high borylation/silylation ratios. Selective reaction of the sterically less‐hindered C?Br bond of dibromoarenes provided monoborylated products. This reaction was used to rapidly construct a D‐π‐A aryl dimesityl borane with a non‐symmetrical biphenyl spacer.     

Fragmentation reactions of optically active trisubstituted cyclopropylcarbinyl radicals.

Fragmentation reactions of optically active trisubstituted cyclopropylcarbinyl radicals and their application to the synthesis of natural products are described. Preparation of the optically pure substrates for radical fragmentation reactions was efficiently accomplished by lipase-mediated desymmetrization of sigma-symmetrical 3-substituted-1,2-cyclopropanedimethanols. In the presence of a radical stabilizing group, e.g., aryl, ester, or alpha,beta-unsaturated ester, the fragmentation occurs selectively to generate the radical on the alpha-carbon of the group and provide the optically pure alkene derivatives. These derivatives possess three chemically distinct functionalities, making them excellent chiral building blocks for the construction of biologically active molecules. The synthetic usefulness of the procedure developed here has been demonstrated by an application to the enantioselective synthesis of both enantiomers of the key intermediate, 4-(3,4-methylenedioxybenzyl)dihydrofuran-2(3H)-one (54), for the total synthesis of biologically active lignans.     

Efficient and enantioselective total syntheses of heliannuols A and K

The second-generation enantioselective synthesis of heliannuol A and the first enantioselective total synthesis of heliannuol K (via two routes) have both been accomplished efficiently; (heliannuol A, nine steps and 25% yield; heliannuol K, seven steps and 47% yield). Highlights of our synthetic strategy include a substrate-controlled chirality transfer in the Lewis acid mediated Claisen rearrangement of the allyl aryl ether for the key construction of a tertiary stereogenic center at the benzylic position followed by, for heliannuol A, ring-closing metathesis, diastereoselective epoxidation, and regioselective cleavage of the epoxide; and for heliannuol K, ring-closing metathesis and conjugate reduction of the eight-membered enone.     

Cyclotron Resonance in the Hidden-Order Phase of URu_{2}Si_{2}

We report the first observation of cyclotron resonance in the hidden-order phase of ultraclean URu_{2}Si_{2} crystals, which allows the full determination of angle-dependent electron-mass structure of the main Fermi-surface sheets. We find an anomalous splitting of the sharpest resonance line under in-plane magnetic-field rotation. This is most naturally explained by the domain formation, which breaks the fourfold rotational symmetry of the underlying tetragonal lattice. The results reveal the emergence of an in-plane mass anisotropy with hot spots along the [110] direction, which can account for the anisotropic in-plane magnetic susceptibility reported recently. This is consistent with the "nematic" Fermi liquid state, in which itinerant electrons have unidirectional correlations.     

Synthesis of substituted 3-iodopyrroles by electrophilic cyclization of propargylic aziridines

The electrophilic cyclization of propargylic aziridines is described. 3-Iodopyrroles having a variety of substituents were conveniently synthesized by the reaction of propargylic aziridines with iodine. The resulting substituted 3-iodopyrrole was further functionalized to the tri-substituted pyrroles with high efficiency.     

A stereoselective route towards heliannuol A

Both epimers of Heliannuol A, first heliannane reported in the literature, isolated from Heliannthus annuus, have been prepared individually in a stereoselective route using a ring closing metathesis (RCM) as a key step to obtain the eight-membered ring. Very good overall yield was obtained in both cases.