A stereocontrolled intramolecular iron-mediated diene/diene tandem double cyclocoupling reaction has been explored using vinyl ethers as the olefin partners. Diastereomerically pure spirotricyclic products with functionalized (alkoxymethyl) side chains can be formed efficiently under photothermal conditions. With a methoxy substituent on the iron-complexed cyclohexadiene core, demetallation and acidic hydrolysis of the cyclocoupling product afforded a cyclohexenone ring.

N-Prolinylanthranilamide-based pseudopeptide organocatalyst 14 was shown to promote enantioselective direct aldol reaction of 7-iodoisatin and 2,2-dimethyl-1,3-dioxan-5-one with 90% conversion (75% isolated yield), 90% enantioselectivity, and 23:1 diastereoselectivity. To demonstrate the synthetic utility of this chemistry, the racemic aldol reaction product was converted in five steps to a potential intermediate for construction of the natural product TMC-95A.

A stereocontrolled intramolecular iron-mediated diene/olefin cyclocoupling reaction has been explored using vinyl ethers as the olefin partners. Spirolactams with functionalized (alkoxymethyl) side chains can be formed under thermal conditions. With a methoxy substituent on the diene, demetalation and hydrolysis of the cyclocoupling product afforded a single diastereomer.

Diels−Alder reactions of cyclopentadienones, to afford substituted biaryls, were studied using an expanded substrate base. Electron-withdrawing groups on the aryl alkyne dienophile facilitated the reaction, and these substrates gave better yields than those with electron-donating substituents. Steric effects were also found to be important, and o,o′-dimethylphenylacetylene gave much poorer yield of biaryl product.

Asymmetric induction during enolate nucleophile addition to chromium tricarbonyl complexes of 4-alkoxy-1-(trimethylsilyl)benzene derivatives, in which the alkoxy group (R*O) is derived from an optically pure alcohol, is analyzed in terms of the effect of the chiral auxiliary (R*) on the conformation of the tricarbonylchromium tripod. Crystal structure determination on the three complexes 3a (R* = 2-phenylisobornyl), 3b (R* = 2-methylisobornyl), and 3c (R* = 2-(3-[1,3]-dioxalanyl)isobornyl) reveals that the chiral group R* causes a rotation of the Cr(CO)3 group from the normally preferred orientation, the extent and direction of which are dependent on the auxiliary. NMR studies on seven complexes indicate the presence of a single conformation in solution for each, which is assumed to be the same as that shown in the solid state. There is a correlation between the observed asymmetric induction and the Cr(CO)3 tripod rotation, which is believed to be a result of the effect of this conformational distortion on the arene-centered FMO coefficients.