Photofixation of CO2 to produce synthetically valuable molecules can be achieved on a photoelectrode based on silicon nanowires. In their Communication on page 6709 ff., K. L. Tan, D. Wang et al. develop a strategy that uses aromatic ketones to receive the photogenerated electrons. The resulting radicals then react with carbon dioxide to afford α-hydroxy acids, which are precursors for the drugs ibuprofen and naproxen. In close resemblance to natural photosynthesis, their strategy gains reaction specificity by avoiding the direct reduction of CO2.

Lights on: When illuminated, p-type Si nanowires donate photogenerated electrons to aromatic ketones, producing reactive radicals that can harvest CO2 to yield α-hydroxy acids (see scheme). The reaction scheme closely resembles that of natural photosynthesis and gives up to 98 % yield and selectivity. Products obtained by this reaction include important precursors for nonsteroidal anti-inflammatory drugs, such as ibuprofen and naproxen. Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Licht an: Beim Bestrahlen übertragen Si-Nanodrähte vom p-Typ photogenerierte Elektronen auf aromatische Ketone, wodurch reaktive Radikale entstehen, die mit CO2 zu α-Hydroxysäuren reagieren (siehe Schema). Das Reaktionsschema mit einer Ausbeute und Selektivität bis 98 % ähnelt stark dem der natürlichen Photosynthese. Zu den auf diesem Weg erhaltenen Produkten gehören wichtige Vorstufen für nichtsteroidale Entzündungshemmer wie Ibuprofen und Naproxen. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Die Photofixierung von CO2 zur Herstellung präparativ wertvoller Moleküle gelingt auf einer Photoelektrode auf Basis von Si-Nanodrähten. In ihrer Zuschrift auf S. 6813 ff. entwickeln K. L. Tan, D. Wang et al. eine Strategie, bei der aromatische Ketone die photogenerierten Elektronen aufnehmen. Die gebildeten Radikale reagieren dann mit CO2 zu α-Hydroxysäuren, Vorstufen der Wirkstoffe Ibuprofen und Naproxen. Ganz ähnlich zur natürlichen Photosynthese gewinnt diese Strategie an Reaktionsspezifität, indem die direkte Reduktion von CO2 vermieden wird.

A highly regioselective hydroformylation of allylic alcohols is reported toward the synthesis of β-hydroxy-acid and aldehyde products. The selectivity is achieved through the use of a ligand that reversibly binds to alcohols in situ, allowing for a directed hydroformylation to occur. The application to trisubstituted olefins was also demonstrated, which yields a single diastereomer product consistent with a stereospecific addition of CO and hydrogen.

ChemInformVolume 42, Issue 9 Preparative Organic Chemistry ChemInform Abstract: Application of a Chiral Scaffolding Ligand in Catalytic Enantioselective Hydroformylation. Amanda D. Worthy, Amanda D. Worthy Dep. Chem., Merkert Chem. Cent., Boston Coll., Chestnut Hill, MA 02467, USASearch for more papers by this authorCandice L. Joe, Candice L. Joe Dep. Chem., Merkert Chem. Cent., Boston Coll., Chestnut Hill, MA 02467, USASearch for more papers by this authorThomas E. Lightburn, Thomas E. Lightburn Dep. Chem., Merkert Chem. Cent., Boston Coll., Chestnut Hill, MA 02467, USASearch for more papers by this authorKian L. Tan, Kian L. Tan Dep. Chem., Merkert Chem. Cent., Boston Coll., Chestnut Hill, MA 02467, USASearch for more papers by this author Amanda D. Worthy, Amanda D. Worthy Dep. Chem., Merkert Chem. Cent., Boston Coll., Chestnut Hill, MA 02467, USASearch for more papers by this authorCandice L. Joe, Candice L. Joe Dep. Chem., Merkert Chem. Cent., Boston Coll., Chestnut Hill, MA 02467, USASearch for more papers by this authorThomas E. Lightburn, Thomas E. Lightburn Dep. Chem., Merkert Chem. Cent., Boston Coll., Chestnut Hill, MA 02467, USASearch for more papers by this authorKian L. Tan, Kian L. Tan Dep. Chem., Merkert Chem. Cent., Boston Coll., Chestnut Hill, MA 02467, USASearch for more papers by this author First published: 03 February 2011 https://doi.org/10.1002/chin.201109051Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume42, Issue9March 1, 2011 RelatedInformation

The synthesis of β-amino-aldehydes has been achieved through enantioselective hydroformylation of PMP-protected allylic amines. The reaction is accomplished by using a scalemic scaffolding ligand that covalently and reversibly binds to the substrate. These ligands behave like chiral auxiliaries because they are covalently attached to the substrate during hydroformylation; however, similar to traditional asymmetric ligands, they can be used in catalytic quantities. The directed hydroformylation of disubstituted olefins occurs under mild conditions (35 °C and 50 psi CO/H(2)), and Z-olefins afford excellent enantioselectivities (up to 93% ee).

The design and application of a scaffolding ligand that promotes branch and diastereoselective hydroformylation of terminal olefins as well as the regio- and diastereoselective hydroformylation of disubstituted olefins is reported. It is shown that the ligand covalently and reversibly bonds to the substrate, allowing for directed hydroformylation. As the substrate ligand interaction is dynamic, hydroformylations are catalytic in ligand and do not require any additional synthetic steps to add or remove the directing group. Using a catalytic quantity of a scaffolding ligand (20-25 mol %), excellent regioselectivity for disubstituted olefins (up to 98:2) and high branch selectivity (up to 88:12) for terminal olefins were obtained.

The design, synthesis, and structure-activity relationship development of naphthalene-derived human CCR8 antagonists is described. In vitro binding assay results of these investigations are reported, critical interactions of the antagonists with CCR8 are defined, and preliminary physicochemical and pharmacokinetic data for the naphthalene scaffold are presented.