Furfural: a renewable and versatile platform molecule for the synthesis of chemicals and fuels
R. Mariscal,  P. Maireles-Torres,  M. Ojeda,  I. Sádabaa and   M. López Granados*

Energy Environ. Sci., 2016, Advance Article

DOI: 10.1039/C5EE02666K
http://pubs.rsc.org/en/content/articlelanding/2016/ee/c5ee02666k#!divAbstract
Received 30 Aug 2015, Accepted 11 Jan 2016
First published online 11 Jan 2016



The production of future transportation fuels and chemicals requires the deployment of new catalytic processes that transform biomass into valuable products under competitive conditions. Furfural has been identified as one of the most promising chemical platforms directly derived from biomass. With an annual production close to 300 kTon, furfural is currently a commodity chemical, and the technology for its production is largely established. The aim of this review is to discuss the most relevant chemical routes for converting furfural to chemicals, biofuels, and additives. This review focuses not only on industrially produced chemicals derived from furfural, but also on other not yet commercialised products that have a high potential for commercialisation as commodities. Other chemicals that are currently produced from oil but can also be derived from furfural are also reviewed. The chemical and engineering aspects such as the reaction conditions and mechanisms, as well as the main achievements and the challenges still to come in the pursuit of advancing the furfural-based industry, are highlighted.

Recent Advances in Process Chemistry

http://pubs.acs.org/doi/pdf/10.1021/acs.oprd.6b00012

Lots of good stuff in this one, below is one example.

Synthesis of 2,3,6-Trisubstituted Pyridines from Isoxazolinones

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Substituted pyridines are an important class of organic compounds and ubiquitous in the chemistry world. Various methodologies have been developed to construct substituted pyridine derivatives. Recently, René Peters and co-workers developed a regioselective Pd-catalyzed synthesis of 2,3,6-trisubstituted pyridines from isoxazolinones (Peters, R., et al. J. Org. Chem. 2015, 80, 6822). The protocol involves a regioselective Pd(II)-catalyzed 1,4-addition of isoxazolinones to enones, followed by a Pd(0)-catalyzed dihydropyridine formation and oxidation. The formation of the dihydropyridine is hypothesized via a vinylnitrene-Pd complex species formed by oxidative addition of Pd(0) to the N–O bond of the 1,4-adduct followed by a decarboxylation. This two-step sequence allows a rapid and regioselective entry to substituted pyridines starting from readily accessible isoxazolinones. Despite these advantages, the safety issue needs to be addressed during application of this approach toward large-scale production as the second step required a mixture of hydrogen and air.

Research Progress on the Indirect Hydrogenation of Carbon Dioxide to Methanol

Xian-Long Du, Zheng Jiang, Dang Shen Su, Jian-Qiang Wang

First published: 21 December 2015   DOI: 10.1002/cssc.201501013

Abstract

Methanol is a sustainable source of liquid fuels and one of the most useful organic chemicals. To date, most of the work in this area has focused on the direct hydrogenation of CO₂ to methanol. However, this process requires high operating temperatures (200–250 °C), which limits the theoretical yield of methanol. Thus, it is desirable to find a new strategy for the efficient conversion of CO₂ to methanol at relatively low reaction temperatures. This Minireview seeks to outline the recent advances on the indirect hydrogenation of CO₂ to methanol. Much emphasis is placed on discussing specific systems, including hydrogenation of CO₂ derivatives (organic carbonates, carbamates, formates, cyclic carbonates, etc.) and cascade reactions, with the aim of critically highlighting both the achievements and remaining challenges associated with this field.

http://onlinelibrary.wiley.com/doi/10.1002/cssc.201501013/full

Conversion of alkanes to linear alkylsilanes using an iridium–iron-catalysed tandem dehydrogenation–isomerization–hydrosilylation

Xiangqing Jia & Zheng Huang

Nature Chemistry Volume: 8, Pages: 157–161  Year published: (2016) doi:10.1038/nchem.2417 Received 04 August 2015    Accepted  11 November 2015  Published online 21 December 2015      

Abstract
The conversion of inexpensive, saturated hydrocarbon feedstocks into value-added speciality chemicals using regiospecific, catalytic functionalization of alkanes is a major goal of organometallic chemistry. Linear alkylsilanes represent one such speciality chemical—they have a wide range of applications, including release coatings, silicone rubbers and moulding products. Direct, selective, functionalization of alkanes at primary C–H bonds is difficult and, to date, methods for catalytically converting alkanes into linear alkylsilanes are unknown. Here, we report a well-defined, dual-catalyst system for one-pot, two-step alkane silylations. The system comprises a pincer-ligated Ir catalyst for alkane dehydrogenation and an Fe catalyst that effects a subsequent tandem olefin isomerization–hydrosilylation. This method exhibits exclusive regioselectivity for the production of terminally functionalized alkylsilanes. This dual-catalyst strategy has also been applied to regioselective alkane borylations to form linear alkylboronate esters.

http://www.nature.com/nchem/journal/v8/n2/full/nchem.2417.html

Reversible Bergman cyclization by atomic manipulation

Bruno Schuler, Shadi Fatayer, Fabian Mohn, Nikolaj Moll, Niko Pavliĉek, Gerhard Meyer, Diego Peña, & Leo Gross

Nature Chemistry Volume: 8, Pages: 220–224 Year published: (2016) doi:10.1038/nchem.2438 Received 20 August 2015 Accepted  11 December 2015 Published online  25 January 2016    

 

Abstract

The Bergman cyclization is one of the most fascinating rearrangements in chemistry, with important implications in organic synthesis and pharmacology. Here we demonstrate a reversible Bergman cyclization for the first time. We induced the on-surface transformation of an individual aromatic diradical into a highly strained ten-membered diyne using atomic manipulation and verified the products by non-contact atomic force microscopy with atomic resolution. The diyne and diradical were stabilized by using an ultrathin NaCl film as the substrate, and the diyne could be transformed back into the diradical. Importantly, the diradical and the diyne exhibit different reactivity, electronic, magnetic and optical properties associated with the changes in the bond topology, and spin multiplicity. With this reversible, triggered Bergman cyclization we demonstrated switching on demand between the two reactive intermediates by means of selective C–C bond formation or cleavage, which opens up the field of radical chemistry for on-surface reactions by atomic manipulation.

 

http://www.nature.com/nchem/journal/v8/n3/full/nchem.2438.html  

A Rhodium–Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques

A Rhodium–Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques

1. Dr. F. Mark Chadwick, 
2. Dr. Nicholas H. Rees, 
3. Prof. Andrew S. Weller, 
4. Dr. Tobias Krämer, 
5. Dr. Marcella Iannuzziand
6. Prof. Stuart A. Macgregor
7. 1. 
      

Authors

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Chadwick, F. M., Rees, N. H., Weller, A. S., Krämer, T., Iannuzzi, M. and Macgregor, S. A. (2016), A Rhodium–Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques. Angew. Chem. Int. Ed..

DOI: 10.1002/anie.201511269

Abstract

The pentane σ-complex [Rh{Cy₂P(CH₂CH₂)PCy₂}(η²:η²-C₅H₁₂)][BAr^F₄] is synthesized by a solid/gas single-crystal to single-crystal transformation by addition of H₂ to a precursor 1,3-pentadiene complex. Characterization by low temperature single-crystal X-ray diffraction (150 K) and SSNMR spectroscopy (158 K) reveals coordination through two Rh⋅⋅⋅H−C interactions in the 2,4-positions of the linear alkane. Periodic DFT calculations and molecular dynamics on the structure in the solid state provide insight into the experimentally observed Rh⋅⋅⋅H−C interaction, the extended environment in the crystal lattice and a temperature-dependent pentane rearrangement implicated by the SSNMR data.

Biaryl Reductive Elimination Is Dramatically Accelerated by Remote Lewis Acid Binding to a 2,2′-Bipyrimidyl–Platinum Complex: Evidence for a Bidentate Ligand Dissociation Mechanism

Biaryl Reductive Elimination Is Dramatically Accelerated by Remote Lewis Acid Binding to a 2,2′-Bipyrimidyl–Platinum Complex: Evidence for a Bidentate Ligand Dissociation Mechanism

Allegra L. Liberman-Martin†, Daniel S. Levine†, Wenjun Liu‡, Robert G. Bergman*†, and T. Don Tilley*†
† Department of Chemistry, University of California−Berkeley, Berkeley, California 94720, United States
‡ Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Organometallics, Article ASAP
DOI: 10.1021/acs.organomet.5b01003
Publication Date (Web): January 4, 2016








The silicon and zinc Lewis acids Si(cat)2 (cat = catecholato), Si(catF)2 (catF = tetrafluorocatecholato), and Zn(C6F5)2 bind to the remote ligand site of a 2,2′-bipyrimidyl–platinum diaryl complex. This platinum complex provides a platform to systematically evaluate electronic and reactivity differences triggered by Lewis acid binding. The electron density of the bipyrimidine ligand is substantially depleted upon Lewis acid binding, as evidenced by UV–vis spectroscopy and cyclic voltammetry. Biaryl reductive elimination studies allowed quantification of the effect of Lewis acid binding on reactivity, and Lewis acid binding accelerated reductive elimination rates by up to 8 orders of magnitude. Kinetics experiments in combination with DFT studies support an unusual mechanism featuring complete dissociation of the Lewis acid-coordinated bidentate bipyrimidine ligand prior to reductive elimination.