https://pubs.rsc.org/en/content/articlepdf/2019/NP/C8NP00092A

Marine natural products.

The conversion of widely available carboxylic acids into versatile boronic esters would be highly enabling for synthesis. We found that this transformation can be effected by illuminating the N-hydroxyphthalimide ester derivative of the carboxylic acid under visible light at room temperature in the presence of the diboron reagent bis(catecholato)diboron. A simple workup allows isolation of the pinacol boronic ester. Experimental evidence suggests that boryl radical intermediates are involved in the process. The methodology is illustrated by the transformation of primary, secondary, and tertiary alkyl carboxylic acids as well as a diverse range of natural-product carboxylic acids, thereby demonstrating its broad utility and functional group tolerance.

/pdf/photoinduced-decarboxylative-borylation-of-carboxylic-acids-4rh5l0k8oa.pdf

Photoinduced decarboxylative borylation of carboxylic acids.

Males and females of nearly all animals differ in their body size, a phenomenon called sexual size dimorphism (SSD). The degree and direction of SSD vary considerably among taxa, including among populations within species. A considerable amount of this variation is due to sex differences in body size plasticity. We examine how variation in these sex differences is generated by exploring sex differences in plasticity in growth rate and development time and the physiological regulation of these differences (e.g., sex differences in regulation by the endocrine system). We explore adaptive hypotheses proposed to explain sex differences in plasticity, including those that predict that plasticity will be lowest for traits under strong selection (adaptive canalization) or greatest for traits under strong directional selection (condition dependence), but few studies have tested these hypotheses. Studies that combine proximate and ultimate mechanisms offer great promise for understanding variation in SSD and sex differences in body size plasticity in insects.

/pdf/sex-differences-in-phenotypic-plasticity-affect-variation-in-45cjtz86dd.pdf

Sex differences in phenotypic plasticity affect variation in sexual size dimorphism in insects: from physiology to evolution.

Olive fruit fly, Bactrocera oleae (Rossi) (Diptera: Tephritidae), is the major pest of commercial olives worldwide. Various aspects of its biology, ecology, management, and impact on olive production are highlighted. With the discovery of insecticidal resistance in some populations frequently treated with organophosphates, old and new control options are being investigated. The potential of biological control is examined. Surveys suggest that a small group of braconids in the Opiinae subfamily best represent the primary parasitoids attacking olive fruit fly in its native range. These species include Psyttalia lounsburyi, P. dacicida, P. concolor, P. ponerophaga, and Utetes africanus. Bracon celer, another braconid but in the Braconinae subfamily, is also reared from the fruit fly in its native range. The potential of these and other natural enemies is discussed with respect to olive fruit fly biology, commercial olive production, and biological constraints that may limit their success. We suggest that numerous species exist that should be further investigated as control agents for olive fruit fly in the many climatic regimes where the pest is found.

Olive Fruit Fly: Managing an Ancient Pest in Modern Times

A novel TEMPO-catalyzed aerobic oxygenation and nitrogenation of hydrocarbons via C═C double-bond cleavage has been disclosed. The reaction employs molecular oxygen as the terminal oxidant and oxygen-atom source by metal-free catalysis under mild conditions. This method can be used for the preparation of industrially and pharmaceutically important N- and O-containing motifs, directly from simple and readily available hydrocarbons.

TEMPO-catalyzed Aerobic Oxygenation and Nitrogenation of Olefins via C═C Double-Bond Cleavage

A simple method for the alkaline hydrolysis of esters

Sulfonamides of homoproline and dipeptides as organocatalysts for Michael and aldol reactions

A general and convenient synthesis of beta-ketols and alpha,beta-alkenones has been achieved by a Knoevenagel condensation of a beta-ketoacid with an aldehyde in aqueous medium. Saponification of a beta-ketoester by an aqueous KOH 10% solution gives the potassium salt of the beta-ketoacid, which is condensed in situ with an aldehyde at pH 7.8-8.0, at 60 degrees C for 5-6 h. The intermediate beta-ketocarboxylate is smoothly decarboxylated in the reaction medium, giving the beta-ketol in high yield (75-90%). Acidification of the reaction mixture at pH 1 and heating at 70 degrees C under vigorous stirring for 6 h, leads directly to the corresponding alpha,beta-unsaturated ketone in good yield (65-75%).

A new protocol for a regioselective aldol condensation as an alternative convenient synthesis of beta-ketols and alpha,beta-unsaturated ketones.

(E)-Alk-3-enoic acids have been prepared in high yield (85–90%) and excellent stereoselectivity (98–99%) by a modified Knoevenagel condensation of a straight carbon chain aldehyde with malonic acid, in dimethyl sulfoxide (DMSO) or dimethylformamide (DMF) at 100 °C, in the presence of piperidinium acetate as catalyst. Condensation of the aldehyde with a monoester of malonic acid, under the above conditions, gave the corresponding ester of (E)-alk-3-enoic acid in high yield (76–82%) and good stereoselectivity (90–92%). Condensation of the aldehyde with cyanoacetic acid gave the β,γ-unsaturated nitrile in moderate yield (35–40%) without stereoselectivity.

Improvement on the synthesis of (E)-alk-3-enoic acids

(+/-)-4-Methyloctanoic acid and its ethyl ester are aggregation pheromones of many rhinoceros beetles of the genus Oryctes and are investigated for the control of these pests by olfactory trapping. A simple, economical, and high-yield (>50%) synthesis of (+/-)-4-methyloctanoic acid and its ethyl ester is presented starting from n-hexanal. The key step in this sequence is an orthoester Claisen rearrangement for the elongation of the carbon chain by two.

Efficient synthesis of (+/-)-4-methyloctanoic acid, aggregation pheromone of rhinoceros beetles of the genus Oryctes (Coleoptera: Dynastidae, Scarabaeidae).

Valentine Ragoussis

Papers

A simple method for the alkaline hydrolysis of esters

Sulfonamides of homoproline and dipeptides as organocatalysts for Michael and aldol reactions

A new protocol for a regioselective aldol condensation as an alternative convenient synthesis of beta-ketols and alpha,beta-unsaturated ketones.

Improvement on the synthesis of (E)-alk-3-enoic acids

Efficient synthesis of (+/-)-4-methyloctanoic acid, aggregation pheromone of rhinoceros beetles of the genus Oryctes (Coleoptera: Dynastidae, Scarabaeidae).