C-F Bond Insertion: An Emerging Strategy for Constructing Fluorinated Molecules.

C-F Insertion reactions, where an organic fragment formally inserts into a carbon-fluorine bond in a substrate, are highly attractive, yet largely unexplored, methods to prepare valuable fluorinated molecules. The inherent strength of C-F bonds and the resulting need for a large thermodynamic driving force to initiate C-F cleavage often leads to sequestering of the released fluoride in an unreactive by-product. Recently, however, several groups have succeeded in overcoming this challenge, opening up the study of C-F insertion as an efficient and highly atom-economical approach to prepare fluorinated compounds. In this article, the recent breakthroughs are discussed focusing on the key conceptual advances that allowed for both C-F bond cleavage and subsequent incorporation of the released fluoride into the product.

Phase Stability of Hexagonal/Cubic Boron Nitride Nanocomposites.

Boron nitride (BN) is an exceptional material, and among its polymorphs, two-dimensional (2D) hexagonal and three-dimensional (3D) cubic BN (h-BN and c-BN) phases are most common. The phase stability regimes of these BN phases are still under debate, and phase transformations of h-BN/c-BN remain a topic of interest. Here, we investigate the phase stability of 2D/3D h-BN/c-BN nanocomposites and show that the coexistence of two phases can lead to strong nonlinear optical properties and low thermal conductivity at room temperature. Furthermore, spark-plasma sintering of the nanocomposite shows complete phase transformation to 2D h-BN with improved crystalline quality, where 3D c-BN possibly governs the nucleation and growth kinetics. Our demonstration might be insightful in phase engineering of BN polymorph-based nanocomposites with desirable properties for optoelectronics and thermal energy management applications.

Formal Insertion of Alkenes Into C(sp3 )-F Bonds Mediated by Fluorine-Hydrogen Bonding.

C-F Insertion reactions represent an attractive approach to prepare valuable fluorinated compounds. The high strength of C-F bonds and the low reactivity of the fluoride released upon C-F bond cleavage, however, mean that examples of such processes are extremely scarce in the literature. Here we report a reaction system that overcomes these challenges using hydrogen bond donors that both activate C-F bonds and allow for downstream reactions with fluoride. In the presence of hexafluoroisopropanol, benzyl and propargyl fluorides undergo efficient formal C-F bond insertion across α-fluorinated styrenes. This process, which does not require any additional fluorinating reagent, occurs under mild conditions and delivers products featuring the gem-difluoro motif, which is attracting increasing interest in medicinal chemistry. Moreover, readily available organic bromides can be engaged directly in a one-pot process that avoids the isolation of organic fluorides.

Comparative evaluation of higher-order aberrations and corneal asphericity between wavefront-guided and aspheric LASIK for myopia.

PURPOSE: To compare visual outcome, higher-order aberrations, and corneal asphericity (Q value) between wavefront-guided and aspheric LASIK for myopia and myopic astigmatism. METHODS: Forty patients were randomly selected to receive wavefront-guided LASIK (wavefront-guided group) or aspheric LASIK (aspheric group) (40 eyes of 20 patients in each group) using the Technolas 217z excimer laser platform (Bausch & Lomb, Rochester, NY). Flaps were created using the Zyoptix XP microkeratome (Bausch & Lomb). Preoperative and postoperative evaluation included uncorrected distance visual acuity (UDVA), corneal topography, wavefront aberrometry, and contrast sensitivity. Minimum follow-up period was 6 months. RESULTS: At 6 months postoperatively, the aspheric group had significantly better UDVA (logMAR 0.04 ± 0.04 [Snellen 20/16] [range: -0.079 to 0.000]) and lower mean residual spherical error (+0.10 ± 0.52 diopters [D] [range: -1.12 to 1.25 D]) than the wavefront-guided group (logMAR UDVA 0.00 ± 0.07 [range: -0.079 to 0.176]; MRSE -0.35 ± 0.47 D [range: -1.5 to 0.62 D]) (P = .003 and < .001, respectively). Mean change in higher-order aberration root mean square at 6 months postoperatively (6-mm pupil) was 0.16 ± 0.17 µm after aspheric LASIK and 0.27 ± 0.28 µm after wavefront-guided LASIK (P = .02). Aspheric LASIK induced minimal change in spherical aberrations postoperatively (0.03 ± 0.12 µm, P = .09), unlike wavefront-guided LASIK (0.23 ± 0.17 µm, P < .01). Change in Q value was significantly less in the aspheric group (0.53 ± 0.31) than the wavefront-guided group (0.91 ± 0.30) (P < .01). The aspheric group had significant improvement in contrast sensitivity at all spatial frequencies (P < .01), whereas the wavefront-guided group showed a slight decrease at higher spatial frequency (18 cycles per degree). CONCLUSIONS: Aspheric LASIK induced significantly less change in higher-order aberrations and maintained corneal asphericity better than wavefront-guided LASIK. The visual outcome and contrast sensitivity was better in the aspheric group at 6 months postoperatively.

Deoxygenative Tri- and Difluoromethylthiolation of Carboxylic Acids with Benzothiazolium Reagents.

Deoxygenative syntheses of fluorinated thioesters directly from carboxylic acids have been developed employing benzothiazolium reagents. The process using BT-SCF3 represents an attractive approach toward these SCF3-containing compounds that avoids the use of metal -SCF3 salts or preactivated acyl electrophiles. Moreover, the in situ activation of BT-SCF2H allows for an unprecedented nucleophilic difluoromethylthiolation reaction. DFT calculations support a mechanistic scenario involving a four-membered transition state where acyl substitution occurs without the formation of an unstable free -SCF2H anion.

Refractive outcome of wavefront guided laser in situ keratomileusis and wavefront guided photorefractive keratectomy in high pre-existing higher order aberration.

PURPOSE: To compare visual outcome and higher order aberrations (HOA) between wavefront-guided LASIK (WF-LASIK) and wavefront guided PRK (WF-PRK) in patients with high preoperative HOA. METHODS: Randomized prospective interventional study. Conducted at Guru Nanak Eye Centre, Maulana Azad Medical College, Delhi, India. Eighty myopic eyes of forty patients were included. INCLUSION CRITERIA: age more than 21 years, best corrected visual acuity of 20/20 or better, a stable refraction, to be off soft contact lens for minimum 14 days prior to preoperative examination, preoperative RMS HOA more than 0.35 µ, preoperative central corneal thickness at least 500 µm, estimated residual stromal bed thickness of at least 275 µm in patients undergoing WF-LASIK and 350 µm in patients undergoing WF-PRK. Exclusion criteria were severe dry eye, blepharitis, corneal disease and warpage, uveitis, posterior segment abnormalities involving the macula or optic nerve and systemic diseases. Patients were randomly divided into two groups. They underwent either WF-LASIK (group A) or WF-PRK (group B) over 2 years (40 eyes each). Patients were followed up for 6 months. Main outcome measures were efficacy, safety, stability, predictability and HOA. RESULTS: At 6 months mean uncorrected visual acuity (logMAR) in group A was -0.01 ± 0.04 and group B was 0.00 ± 0.07 (P = 0.23). HOA RMS (6mm pupil) in group A was 0.61 ± 0.24 µm and group B was 0.55 ± 0.25 µm. The increase was statistically significant in both the groups (P < 0.05). Both the groups showed similar efficacy, predictability and safety. CONCLUSION: WF-LASIK and WF-PRK have similar efficacy, safety and predictability, though WF-PRK induces less HOA.