The [N]phenylenes display marked deformation from planarity in the crystalline state. In order to probe the generality of this phenomenon, several derivatives were synthesized and their single-crystal X-ray structures were obtained. All new compounds displayed some degree of nonplanarity. Thus, for example, the parent triangular [4]phenylene (4 b) has a median bend angle at the ring junction of 1.58 and a range of 0.38 to 3.58, whereas hexakis[triisopropylsilyl(ethynyl)] triangular [4]phenylene (4 c) possesses the bulkiest appendages and the largest median bend angle and range (3.88 and 1.78 ± 5.68, respectively). A detailed analysis of the bending and twisting angles at the ring junctions, however, revealed that the magnitude of deformations were independent of topology, molecular size, and substituent type. In contrast to the phenylenes, a Cambridge Structural Database (CSD) search of unsubstituted and non-peri-substituted naphthalenes and anthracenes shows these molecules to be virtually planar in the solid state. A comparison of the single-point energies (HF/6-31G*) of the phenylenes with the acenes calculated for molecules possessing a fixed bend angle at the ring fusion of 38, 68, 98, and 128 reveals the former to be 26 % to 45 % easier to deform than the latter. Based on these results, the nonplanarity seen for the phenylenes is most likely a consequence of crystalpacking forces deforming particularly flexible molecules.

Arylboron compounds have intriguing properties and are important building blocks for chemical synthesis. A family of Ir catalysts now enables the direct synthesis of arylboron compounds from aromatic hydrocarbons and boranes under "solventless" conditions. The Ir catalysts are highly selective for C-H activation and do not interfere with subsequent in situ transformations, including Pd-mediated cross-couplings with aryl halides. By virtue of their favorable activities and exceptional selectivities, these Ir catalysts impart the synthetic versatility of arylboron reagents to C-H bonds in aromatic and heteroaromatic hydrocarbons.

Glandular secreting trichomes of cultivated tomato (Solanum lycopersicum) and close relatives produce a variety of structurally diverse volatile and non-volatile specialized (‘secondary’) metabolites, including terpenes, flavonoids and acyl sugars. A genetic screen is described here to profile leaf trichome and surface metabolite extracts of nearly isogenic chromosomal substitution lines covering the tomato genome. These lines contain specific regions of the Solanum pennellii LA0716 genome in an otherwise ‘wild-type’ M82 tomato genetic background. Regions that have an impact on the total amount of extractable mono- and sesquiterpenes (IL2-2) or only sesquiterpenes (IL10-3) or specifically influence accumulation of the monoterpene α-thujene (IL1-3 and IL1-4) were identified using GC-MS. A rapid LC-TOF-MS method was developed and used to identify changes in non-volatile metabolites through non-targeted analysis. Metabolite profiles generated using this approach led to the discovery of introgression lines producing different acyl chain substitutions on acyl sugar metabolites (IL1-3/1-4 and IL8-1/8-1-1), as well as two regions that influence the quantity of acyl sugars (IL5-3 and IL11-3). Chromosomal region 1-1/1-1-3 was found to influence the types of glycoalkaloids that are detected in leaf surface extracts. These results show that direct chemical screening is a powerful way to characterize genetic diversity in trichome specialized metabolism.

An efficient one-pot C-H activation/borylation/oxidation protocol for the preparation of phenols is described. This method is particularly attractive for the generation of meta-substituted phenols bearing ortho-/para-directing groups, as such substrates are difficult to access by other phenol syntheses.

Ir-catalyzed borylation of 2-substituted indoles selectively yields 7-borylated products in good yields. N-Protection, required for previous functionalizations of 2-substituted indoles, is unnecessary.