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• 57576-09-7 (1R,2S,5R)-5-methyl-2-(prop-1-en-2-yl)cyclohexyl acetate 
• 2623-23-6 L-menthyl acetate 

Relevant academic research and scientific papers

Low-Spin and High-Spin Perferryl Intermediates in Non-Heme Iron Catalyzed Oxidations of Aliphatic C?H Groups

The selectivity patterns of iron catalysts of the Fe(PDP) family in aliphatic C?H oxidation with H2O2 have been studied (PDP=N,N′-bis(pyridine-2-ylmethyl)-2,2′-bipyrrolidine). Cyclohexane, adamantane, 1-bromo-3,7-dimethyloctane, 3,7-

N-Ammonium Ylide Mediators for Electrochemical C-H Oxidation

The site-specific oxidation of strong C(sp3)-H bonds is of uncontested utility in organic synthesis. From simplifying access to metabolites and late-stage diversification of lead compounds to truncating retrosynthetic plans, there is a growing need for new reagents and methods for achieving such a transformation in both academic and industrial circles. One main drawback of current chemical reagents is the lack of diversity with regard to structure and reactivity that prevents a combinatorial approach for rapid screening to be employed. In that regard, directed evolution still holds the greatest promise for achieving complex C-H oxidations in a variety of complex settings. Herein we present a rationally designed platform that provides a step toward this challenge using N-ammonium ylides as electrochemically driven oxidants for site-specific, chemoselective C(sp3)-H oxidation. By taking a first-principles approach guided by computation, these new mediators were identified and rapidly expanded into a library using ubiquitous building blocks and trivial synthesis techniques. The ylide-based approach to C-H oxidation exhibits tunable selectivity that is often exclusive to this class of oxidants and can be applied to real-world problems in the agricultural and pharmaceutical sectors.

Direct Oxidation of Csp3?H bonds using in Situ Generated Trifluoromethylated Dioxirane in Flow

A fast, scalable, and safer Csp3?H oxidation of activated and un-activated aliphatic chains can be enabled by methyl(trifluoromethyl)dioxirane (TFDO). The continuous flow platform allows the in situ generation of TFDO gas and its rapid reactivity toward tertiary and benzylic Csp3?H bonds. The process exhibits a broad scope and good functional group compatibility (28 examples, 8–99 %). The scalability of this methodology is demonstrated on 2.5 g scale oxidation of adamantane.

Efficient Aliphatic C?H Bond Oxidation Catalyzed by Manganese Complexes with Hydrogen Peroxide

A tetradentate nitrogen ligand containing a benzimidazole ring and an electron-rich pyridine ring was developed, the resulting manganese complex exhibited good activity in the C?H oxidation of simple alkanes. In particular, cyclic aliphatic alkanes were transformed into ketones in very good yields (up to 89 %) by using environmentally benign H2O2 as the terminal oxidant. This protocol was also applied successfully in benzylic C?H oxidation, giving the corresponding ketones with very good selectivities. In addition, tertiary C?H bond oxidation of complex molecules by the manganese complex showed potential utility for assembling alcohols with good selectivity in late-stage chemical synthesis.

Supramolecular recognition allows remote, site-selective C-H oxidation of methylenic sites in linear amines

Site-selective C-H functionalization of aliphatic alkyl chains is a longstanding challenge in oxidation catalysis, given the comparable relative reactivity of the different methylenes. A supramolecular, bioinspired approach is described to address this challenge. A Mn complex able to catalyze C(sp3)-H hydroxylation with H2O2 is equipped with 18-benzocrown-6 ether receptors that bind ammonium substrates via hydrogen bonding. Reversible pre-association of protonated primary aliphatic amines with the crown ether selectively exposes remote positions (C8 and C9) to the oxidizing unit, resulting in a site-selective oxidation. Remarkably, such control of selectivity retains its efficiency for a whole series of linear amines, overriding the intrinsic reactivity of C- H bonds, no matter the chain length.

Iron Complex Catalyzed Selective C-H Bond Oxidation with Broad Substrate Scope

The use of a peroxidase-mimicking Fe complex has been reported on the basis of the biuret-modified TAML macrocyclic ligand framework (Fe-bTAML) as a catalyst to perform selective oxidation of unactivated 3° C-H bonds and activated 2° C-H bonds with low catalyst loading (1 mol %) and high product yield (excellent mass balance) under near-neutral conditions and broad substrate scope (18 substrates which includes arenes, heteroaromatics, and polar functional groups). Aliphatic C-H oxidation of 3° and 2° sites of complex substrates was achieved with predictable selectivity using steric, electronic, and stereoelectronic rules that govern site selectivity, which included oxidation of (+)-artemisinin to (+)-10β-hydroxyartemisinin. Mechanistic studies indicate FeV(O) to be the active oxidant during these reactions.

Non-Heme Iron Catalysts with a Rigid Bis-Isoindoline Backbone and Their Use in Selective Aliphatic C?H Oxidation

Iron complexes derived from a bis-isoindoline-bis-pyridine ligand platform based on the BPBP ligand (BPBP=N,N′-bis(2-picolyl)-2,2′-bis-pyrrolidine) have been synthesized and applied in selective aliphatic C?H oxidation with hydrogen peroxide under mild conditions. The introduction of benzene moieties on the bis-pyrrolidine backbone leads to an increased preference of tertiary over secondary C?H bond oxidation (3°/2° ratio up to 33). On the other hand, substituting the meta-position of the pyridines with bulky silyl groups affords enhanced secondary C?H oxidation selectivity and generally leads to higher product yields and mass balances. (Figure presented.).

Highly efficient, regioselective, and stereospecific oxidation of aliphatic C-H groups with H2O2, catalyzed by aminopyridine manganese complexes

Aminopyridine manganese complexes [LMnII(OTf)2] having a similar coordination topology catalyze the oxidation of unactivated aliphatic C-H groups with H2O2, demonstrating excellent efficiency (up to TON = 970), site selectivity, and stereospecificity (up to >99%).

Selective Aliphatic C-H Oxidation

A composition including a complex of a metal, a tetradentate ligand, at least one ancillary ligand, and a counterion may be used for selective sp3 C—H bond oxidation. The tetradentate ligand may include a N-heterocyclic-N,N′-bis(pyridyl)-ethane-1,2-diamine group or a N,N′-bis(heterocyclic)-N,N′-bis(pyridyl)-ethane-1,2-diamine group. The composition can be used in combination with H2O2 to effect highly selective oxidations of unactivated sp3 C—H bonds over a broad range of substrates. The site of oxidation can be predicted, based on the electronic and/or steric environment of the C—H bond. In addition, the oxidation reaction does not require the presence of directing groups in the substrate.

The Fe(PDP)-catalyzed aliphatic C-H oxidation: a slow addition protocol

This report describes a slow addition protocol for the Fe(PDP)-catalyzed aliphatic C-H oxidation reaction. Under this protocol, the reaction can be productively driven to higher conversions without decreasing site-selectivity or chemoselectivity. The operational advantages of this procedure are highlighted in the oxidation of two complex natural product derivatives. Hydroxylated products can be obtained in high isolated yields without the need for recycling recovered starting materials.