Correction: Ring-opening yields and auto-oxidation rates of the resulting peroxy radicals from OH-oxidation of α-pinene and ß-pinene.

[This corrects the article DOI: 10.1039/D2EA00133K.].

Organic synthesis in the study of terpene-derived oxidation products in the atmosphere.

Covering: 1997 up to 2022Volatile biogenic terpenes involved in the formation of secondary organic aerosol (SOA) particles participate in rich atmospheric chemistry that impacts numerous aspects of the earth's complex climate system. Despite the importance of these species, understanding their fate in the atmosphere and determining their atmospherically-relevant properties has been limited by the availability of authentic standards and probe molecules. Advances in synthetic organic chemistry directly aimed at answering these questions have, however, led to exciting discoveries at the interface of chemistry and atmospheric science. Herein we provide a review of the literature regarding the synthesis of commercially unavailable authentic standards used to analyze the composition, properties, and mechanisms of SOA particles in the atmosphere.

Large Gas-Phase Source of Esters and Other Accretion Products in the Atmosphere.

Dimeric accretion products have been observed both in atmospheric aerosol particles and in the gas phase. With their low volatilities, they are key contributors to the formation of new aerosol particles, acting as seeds for more volatile organic vapors to partition onto. Many particle-phase accretion products have been identified as esters. Various gas- and particle-phase formation pathways have been suggested for them, yet evidence remains inconclusive. In contrast, peroxide accretion products have been shown to form via gas-phase peroxy radical (RO2) cross reactions. Here, we show that these reactions can also be a major source of esters and other types of accretion products. We studied α-pinene ozonolysis using state-of-the-art chemical ionization mass spectrometry together with different isotopic labeling approaches and quantum chemical calculations, finding strong evidence for fast radical isomerization before accretion. Specifically, this isomerization seems to happen within the intermediate complex of two alkoxy (RO) radicals, which generally determines the branching of all RO2-RO2 reactions. Accretion products are formed when the radicals in the complex recombine. We found that RO with suitable structures can undergo extremely rapid C-C ß scissions before recombination, often resulting in ester products. We also found evidence of this previously overlooked RO2-RO2 reaction pathway forming alkyl accretion products and speculate that some earlier peroxide identifications may in fact be hemiacetals or ethers. Our findings help answer several outstanding questions on the sources of accretion products in organic aerosol and bridge our knowledge of the gas phase formation and particle phase detection of accretion products. As esters are inherently more stable than peroxides, this also impacts their further reactivity in the aerosol.

Concise Synthesis of Annulated Pyrido[3,4-b]indoles via Rh(I)-Catalyzed Cyclization.

The synthesis of pyridines bearing multiple ring fusions poses a considerable challenge for organic chemists. To address this problem, we describe the synthesis of a small library of pyrido[3,4-b]indoles via an efficient, five-step sequence. The key transformation is a Rh(I)-catalyzed [2 + 2 + 2] cyclization that forms three rings in one reaction flask. Our method is high yielding, accommodates a variety of functional groups, and suffers no entropic costs as ring size increases.

Three-step synthesis of an annulated ß-carboline via palladium catalysis.

The synthesis of ß-carbolines is a mature field, yet new methods are desirable to introduce new functionality onto the core scaffold. We describe the incorporation of an additional fused ring onto the ß-carboline via a novel palladium-catalyzed, one-pot Sonogashira coupling/intramolecular [2+2+2] cyclization. This method generates three rings in one flask and produces an annulated ß-carboline in 80% yield. A preliminary mechanistic study into the sequence of events is described, which confirms an unprecedented catalytic role for palladium.