Valorization of Biomass Derived Terpene Compounds by Catalytic Amination

Abstract

This review fills an apparent gap existing in the literature by providing an overview of the readily available terpenes and existing catalytic protocols for preparation of terpene-derived amines. To address the role of solid catalysts in amination of terpenes the same reactions with homogeneous counterparts are also discussed. Such catalysts can be considered as a benchmark, which solid catalysts should match. Although catalytic systems based on transition metal complexes have been developed for synthesis of amines to a larger extent, there is an apparent need to reduce the production costs. Subsequently, homogenous systems based on cheaper metals operating by nucleophilic substitution (e.g., Ni, Co, Cu, Fe) with a possibility of easy recycling, as well as metal nanoparticles (e.g., Pd, Au) supported on amphoteric oxides should be developed. These catalysts will allow synthesis of amine derivatives of terpenes which have a broad range of applications as specialty chemicals (e.g., pesticides, surfactants, etc.) and pharmaceuticals. The review will be useful in selection and design of appropriate solid materials with tailored properties as efficient catalysts for amination of terpenes.

Corymbia citriodora: A Valuable Resource from Australian Flora for the Production of Fragrances, Repellents, and Bioactive Compounds

“…The cyclization of citronellal (1) to isopulegol (2) is an important step in the process of producing (-)-menthol (7). Natural sources of 7 are the leaves of Mentha arvensis and other mint species, but 7 may contain a mixture of different diastereoisomers such as neoisomenthol (8), isomenthol (9), and neomenthol (10) (Scheme 2) [49]. Although the most abundant form of 7 in nature is (-)-7, producing isomer-free and enantiopure (-)-7 synthetically in large quantities poses a challenge as only (-)-7 is valued for its pharmaceutical qualities [50].…”

“…citronellal, citronellol, and isopulegol, which has not been specifically reviewed. While several of the terpenes present in LSG oil have been highlighted in reviews as important precursors in their own right for the further synthesis of more complex organic molecules [5,6], bioactive compounds [7], pheromones [5], or for increasing the value of the compounds through further synthesis [8], this review has instead focused on relevant industrial processes pertinent to LSG terpenes, followed by a more general summation of the most recent advances involving these terpenes in synthesis related to fragrances, repellents and related compounds, as well as bioactive drug synthesis. A special focus was placed on the use of green chemistry practices [9].…”

Cycloamination strategies for renewable N-heterocycles

“…31 Given the above considerations, urgent attention is needed to develop green and efficient approaches to task-specific azaheterocycles from renewable biomass feedstocks via sustainable chemistry. The employed nitrogen sources can be derived from ammonia, amines/amides pre-prepared by C-N coupling reactions (e.g., reductive amination, aminolysis, and amidation), [32][33][34][35][36] or natural N-reservoirs (e.g., chitin, proteins) for producing amines and derivatives (e.g., glucosamine, N-acetyl-D-glucosamine, amino acids). [37][38][39][40][41] Beginning from the accessible bio-based functional molecules, N-heterocycles can be constructed by C-N and/or C-C bond formation typically via three dominant synthetic routes including intramolecular cyclization, cycloaddition (e.g., aza-Diels-Alder), and multicomponent condensation reactions (Fig.…”

Regeneration of Raney®-Nickel Catalyst for the Synthesis of High-Value Amino-Ester Renewable Monomers

“…Since the discovery of Ni(CO) 4 complexes by Mond in 1888 [1], organo-nickel chemistry saw comprehensive developments. Nickel-based catalysts proved their effectiveness in several types of reactions, including cross-couplings [2], methanations [3,4], nucleophilic allylations [5,6], oligomerizations [7], hydrodeoxygenations [8], and hydrogenations [9]. This last reaction can make use of Raney ® -nickel, which is the most popular catalyst in the field.…”