Polyols and polyacrylates have a wide range of applications in polymer synthesis as monomers, initiators, or building blocks in a variety of polymerization reaction types. With an ever‐growing need ...to reduce the global dependency on fossil fuels, finding bio‐based/renewable sources for these compounds is now critical. Herein, the alkene moieties of common, abundant terpenes are functionalized via oxidation to expand the “toolbox” of bio‐based diols and triols. These polyol compounds are readily converted into the corresponding terpene‐derived diacrylates using mild conditions. As a proof of concept, it is demonstrated that these monomers can be used in aza‐Michael polymerizations, forming new (bio)degradable poly‐β‐amino esters.
With an ever‐growing need to reduce the global dependency on fossil fuels, finding bio‐based/renewable sources is now critical. Herein, the alkene moieties of abundant terpenes are functionalized via oxidation to expand the “toolbox” of bio‐based diols/triols. These polyol compounds are readily converted into the corresponding terpene‐derived diacrylates using mild conditions and polymerized via aza‐Michael polymerizations, forming new (bio)degradable poly‐β‐amino esters.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Terpene and terpenoid cyclizations are counted among the most complex chemical reactions occurring in nature and contribute crucially to the tremendous structural diversity of this largest family of ...natural products. Many studies were conducted at the chemical, genetic, and biochemical levels to gain mechanistic insights into these intriguing reactions that are catalyzed by terpene and terpenoid cyclases. A myriad of these enzymes have been characterized. Classical textbook knowledge divides terpene/terpenoid cyclases into two major classes according to their structure and reaction mechanism. However, recent discoveries of novel types of terpenoid cyclases illustrate that nature’s enzymatic repertoire is far more diverse than initially thought. This Review outlines novel terpenoid cyclases that are out of the ordinary.
Terpene and terpenoid cyclizations are counted among the most complex chemical reactions occurring in nature and contribute crucially to the tremendous structural diversity of this largest family of natural products. This Review outlines novel terpenoid cyclases (TCs) beyond typical class I and II TCs, and showcases how their intriguing reaction mechanisms can inspire synthetic chemistry.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The hydration of camphene was carried out over SBA-15 with sulfonic acid groups and tungstophosphoric acid at 50 °C. The main product of camphene hydration was isoborneol, with camphene hydrate and ...borneol as byproducts. The catalytic activity increased with the amount of tungstophosforic acid (PW) immobilized on the silica support until a maximum, which was obtained with the PW4-SBA-15-SOsub.3H material (16.4 wt.%). When the amount of PW immobilized on SBA-15 increased (PW5-SBA-15-SOsub.3H, 21.2 wt.%), the catalytic activity decreased. The catalytic activity of PW4-SBA-15-SOsub.3H increased with the water content of the solvent, until a maximum was reached with 50% water. With higher water concentrations, a decrease in the catalytic activity was observed. The selectivity to isoborneol was 90% at 99% camphene conversion in the presence of the PW4-SBA-15-SOsub.3H catalyst. The catalytic stability of the PW4-SBA-15-SOsub.3H material during camphene hydration was studied by performing consecutive batch runs with the same catalyst sample. After the third run, a trend towards stabilized catalytic activity was observed. A kinetic model is also proposed.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
The development of sustainable renewable polymers from natural resources has increasingly gained attention from scientists, engineers as well as the general public and government agencies. This ...review covers recent progress in the field of renewable bio‐based monomers and polymers from natural resources: terpenes, terpenoids, and rosin, which are a class of hydrocarbon‐rich biomass with abundance and low cost, holding much potential for utilization as organic feedstocks for green plastics and composites. This review details polymerization and copolymerization of terpenes such as pinene, limonene, and myrcene and their derivatives, terpenoids including carvone and menthol, and rosin‐derived monomers. The future direction on the utilization of these natural resources is discussed.
A review on recent advances in the development of renewable monomers and polymers from natural resources terpenes, terpenoids, and rosin is covered. A variety of polymerization techniques and post‐polymerization modification methods are reviewed in the preparation of sustainable renewable polymers and composites.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The pool of abundant chiral terpene building blocks (i.e., “chiral pool terpenes”) has long served as a starting point for the chemical synthesis of complex natural products, including many terpenes ...themselves. As inexpensive and versatile starting materials, such compounds continue to influence modern synthetic chemistry. This review highlights 21st century terpene total syntheses which themselves use small, terpene-derived materials as building blocks. An outlook to the future of research in this area is highlighted as well.
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IJS, KILJ, NUK, PNG, UL, UM
Terpenes are the primary constituents of essential oils and are responsible for the aroma characteristics of cannabis. Together with the cannabinoids, terpenes illustrate synergic and/or entourage ...effect and their interactions have only been speculated in for the last few decades. Hundreds of terpenes are identified that allude to cannabis sensory attributes, contributing largely to the consumer's experiences and market price. They also enhance many therapeutic benefits, especially as aromatherapy. To shed light on the importance of terpenes in the cannabis industry, the purpose of this review is to morphologically describe sources of cannabis terpenes and to explain the biosynthesis and diversity of terpene profiles in different cannabis chemovars.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Natural products obtained in dietary components may aid the prevention and treatment of a variety of diseases. Reports in the scientific literature have demonstrated that the consumption of terpenes ...is a successful alternative in the treatment of several diseases, triggering beneficial biological effects in clinical and preclinical studies. The monoterpene limonene is largely used in alimentary items, cleaning products, and it is one of the most frequent fragrances used in cosmetics formulation. The therapeutic effects of limonene have been extensively studied, proving anti-inflammatory, antioxidant, antinociceptive, anticancer, antidiabetic, antihyperalgesic, antiviral, and gastroprotective effects, among other beneficial effects in health. In this review, we collected, presented, and analyzed evidence from the scientific literature regarding the usage of limonene and its activities and underlying mechanisms involved in combating diseases. The highlighting of limonene applications could develop a useful targeting of innovative research in this field as well as the development of a limonene-based phytomedicine which could be used in a variety of conditions of health and disease.
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•This review article reports biological effects offered by limonene.•Limonene modulates the production of cytokines.•Limonene can modulate signaling pathways linked to several diseases.•Limonene can be used as diet supplementation by humans.•Future clinical studies can be developed considering preclinical results reported.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPUK, ZRSKP
The presence of a quaternary centre-a carbon with four other carbons bonded to it-in any given molecule can have a substantial chemical and biological impact. In many cases, it can enable otherwise ...challenging chemistry. For example, quaternary centres induce large rate enhancements in cyclization reactions-known as the Thorpe-Ingold effect-which has application in drug delivery for molecules with modest bioavailability
. Similarly, the addition of quaternary centres to a drug candidate can enhance both its activity and its metabolic stability
. When present in chiral ligands
, catalysts
and auxiliaries
, quaternary centres can guide reactions toward both improved and unique regio-, stereo- and/or enantioselectivity. However, owing to their distinct steric congestion and conformational restriction, the formation of quaternary centres can be achieved reliably by only a few chemical transformations
. For particularly challenging cases-for example, the vicinal all-carbon
, oxa- and aza-quaternary centres
in molecules such as azadirachtin
, scopadulcic acid A
and acutumine
-the development of target-specific approaches as well as multiple functional-group and redox manipulations is often necessary. It is therefore desirable to establish alternative ways in which quaternary centres can positively affect and guide synthetic planning. Here we show that if a synthesis is designed such that each quaternary centre is deliberately leveraged to simplify the construction of the next-either through rate acceleration or blocking effects-then highly efficient, scalable and modular syntheses can result. This approach is illustrated using the conidiogenone family of terpenes as a representative case; however, this framework provides a distinct planning logic that is applicable to other targets of similar synthetic complexity that contain multiple quaternary centres.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
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