Xylochemicals and where to find them

This article surveys a range of important platform and high value chemicals that may be considered primary and secondary 'xylochemicals'. A summary of identified xylochemical substances and their natural sources is provided in tabular form. In detail, this review is meant to provide useful assistance for the consideration of potential synthetic strategies using xylochemicals, new methodologies and the development of potentially sustainable, xylochemistry-based processes. It should support the transition from petroleum-based approaches and help to move towards more sustainability within the synthetic community. This feasible paradigm shift is demonstrated with the total synthesis of natural …

An Efficient Synthesis of Tenofovir (PMPA): A Key Intermediate Leading to Tenofovir-Based HIV Medicines

Abstract: Herein, we report further improvements to the synthesis of tenofovir 1, the precursor to tenofovir disoproxil fumarate and tenofovir alafenamide fumarate. Starting from acyclic precursor diaminomalononitrile 12, a four-step protocol to tenofovir 1 will allow for vertical integration for more manufacturers. The key transformation is a more convergent one step procedure from 6 as compared to the current commercial process, with an improved yield from 59% (two steps) to 70%. Further improvements include eliminating the need for problematic magnesium tert-butoxide (MTB) and significant solvent reduction by eliminating the need for an intermediate workup. With the costs of HIV/AIDS tre…

Xylochemie – Naturstoffsynthese aus Holz

Synthesis of 5‐Fluorocytosine Using 2‐Cyano‐2‐fluoroethenolate as a Key Intermediate

Titelbild: Xylochemie – Naturstoffsynthese aus Holz (Angew. Chem. 47/2015)

Asymmetric One-Pot Synthesis of (3R,3aS,6aR)-Hexahydrofuro[2,3-b]furan-3-ol: A Key Component of Current HIV Protease Inhibitors

A concise and efficient synthesis of (3R,3aS,6aR)-hexahydrofuro[2,3-b]furan-3-ol, a key building block for several clinical and experimental HIV protease inhibitors including the highly important drug darunavir, was achieved via a one-pot procedure using furan and Cbz-protected glycol aldehyde as starting materials. A [2+2]-photocycloaddition between both reactants which can be prepared from wood-based starting materials according to the principles of xylochemistry, followed by hydrogenation and lipase-catalyzed kinetic resolution afforded the target compound in high yield and up to 99% ee.

Cover Picture: Xylochemistry-Making Natural Products Entirely from Wood (Angew. Chem. Int. Ed. 47/2015)

Examples of xylochemistry: colorants and polymers

Against the backdrop of modern sustainable chemistry and valorization of biomass for chemical raw materials, the syntheses of indigo dyes and polyamides as representatives of two classes of everyday chemical products based on xylochemicals are described. Wood-derived starting materials were transformed into functional materials using the principles of green chemistry to expand the scope of products gained from renewable resources. The indigo dyes were synthesized in a short, straightforward sequence starting from vanillin. Two polyamides, representatives of an important class of polymers, were obtained from 4-propylcyclohexanol, which is one of the longest known (and most abundant) hydrogen…

Xylochemistry--Making Natural Products Entirely from Wood.

The first total synthesis of the dimeric berberine alkaloid ilicifoline (ilicifoline B) is reported. Its carbon skeleton is constructed from ferulic acid, veratrole, and methanol. The synthesis reported herein employs starting materials solely derived from wood. The natural product is thus constructed entirely from renewable resources. The same strategy is applied to a formal total synthesis of morphinan alkaloids. The use of wood-derived building blocks (xylochemicals) instead of the conventional petrochemicals represents a sustainable alternative to classical synthetic approaches.

Synthesis of Highly Substituted 2-13C-Imidazolium Salts and Metal NHC ­Complexes for the Investigation of Electronic Unsymmetry by NMR

Complexes of unsymmetrically substituted N-heterocyclic carbenes with NMR-active metals (Ag, Hg, Pt) with or without a 13C-label in the 2-position were synthesized by aldimine cross coupling and analyzed with respect to the scalar couplings between the metal center or C2 and the other ring atoms.