Darren Poole

Silver hammer: The silver-catalyzed decarboxylative arylation of electron-deficient (hetero)arenes has been successfully developed using aromatic carboxylic acids as arylating reagents. For most of aromatic carboxylic acids evaluated, 5 mol % of the silver(I) salt was enough for the oxidative decarboxylation. An ortho substituent was not necessary for this decarboxylative cross-coupling protocol.

[Communication]
Jian Kan, Shijun Huang, Jin Lin, Min Zhang, Weiping Su
Angew. Chem. Int. Ed., December 23, 2014, DOI: 10.1002/anie.201408630. Read article.

The mediator: A rationally designed myoglobin (Mb) catalyst capable of promoting the cyclopropanation of a range of aryl-substituted olefins with high catalytic activity and excellent diastereo- and enantioselectivity is reported. These studies define myoglobin as a promising and robust scaffold for mediating carbene-transfer reactions.

[Communication]
Melanie Bordeaux, Vikas Tyagi, Rudi Fasan
Angew. Chem. Int. Ed., December 23, 2014, DOI: 10.1002/anie.201409928. Read article.

Competitive coordination: Chiral γ-secondary-amino alcohols were obtained in high yields and with excellent enantioselectivities by hydrogenation of β-secondary-amino ketones. NMR spectroscopy and HRMS are used to investigate the mechanism for the activation effect of ZnCl₂ on the bisphosphine–rhodium catalyst.

[Communication]
Qiupeng Hu, Zhenfeng Zhang, Yangang Liu, Tsuneo Imamoto, Wanbin Zhang
Angew. Chem. Int. Ed., December 29, 2014, DOI: 10.1002/anie.201411384. Read article.

On loan: [{Ir(cod)Cl}₂] facilitates hydrogen-borrowing reactions of ketone enolates with methanol at 65 °C as described. Performing the reaction under an oxygen atmosphere aids the process, and when combined with a bulky monodentate phosphine ligand, interrupts the catalytic cycle by preventing enone reduction. The addition of pro-nucleophiles to the reaction mixture completes a one-pot methylenation/conjugate addition protocol.

[Communication]
Di Shen, Darren L. Poole, Camilla C. Shotton, Anne F. Kornahrens, Mark P. Healy, Timothy J. Donohoe
Angew. Chem. Int. Ed., December 9, 2014, DOI: 10.1002/anie.201410391. Read article.

Readily available 2-hydroxypyridines are converted into enantioenriched N-substituted 2-pyridone derivatives by means of a highly efficient protocol. The title reaction features a good tolerance of functional groups in both the allylic carbonates and 2-hydroxypyridines, thus delivering multifunctionalized heterocyclic products with up to 98 % yield and 99 % ee. cod=1,5-cyclooctadiene.

[Communication]
Xiao Zhang, Ze-Peng Yang, Lin Huang, Shu-Li You
Angew. Chem. Int. Ed., December 12, 2014, DOI: 10.1002/anie.201409976. Read article.

Paired off: A new strategy, which combines a chiral phosphine with methyl acrylate to form a homogeneous ion pair, is introduced. This activation mode has been successfully applied to Mannich-type reactions, thus generating a variety of fluorinated amino acid derivatives in high yields and with high ee values.

[Communication]
Hong-Yu Wang, Kai Zhang, Chang-Wu Zheng, Zhuo Chai, Dong-Dong Cao, Jia-Xing Zhang, Gang Zhao
Angew. Chem. Int. Ed., December 16, 2014, DOI: 10.1002/anie.201409342. Read article.

A bit tangy: The Rh/TangPhos-catalyzed asymmetric hydrogenation of α,γ-dienamido esters has been developed and affords γ,δ-unsaturated amido esters with both high regioselectivities and enantioselectivities. This protocol furnishes products using a high substrate to catalyst ratio (S/C) and with greater than 99 % ee. This strategy had been applied in the asymmetric synthesis of key a precursor to Ramipril, an ACE inhibitor. cod=1,5-cyclooctadiene.

[Communication]
Min Gao, Jing-jing Meng, Hui Lv, Xumu Zhang
Angew. Chem. Int. Ed., December 15, 2014, DOI: 10.1002/anie.201410213. Read article.

High yield and productivity is achieved for the synthesis of heterocyclic thioquinazolinones by sequential reaction in a one-flow microreactor. This methodology allows control of the residence time of reactive intermediates and significantly speeds up reaction times.

[Communication]
Heejin Kim, Hyune-Jea Lee, Dong-Pyo Kim
Angew. Chem. Int. Ed., December 17, 2014, DOI: 10.1002/anie.201410062. Read article.

Lewis and Brønsted at play: Simple cyclohexa-1,4-dienes with suitably positioned donor substituents in the 1,5-positions serve as reducing agents in the title reaction (see scheme). B(C₆F₅)₃ is sufficiently Lewis acidic to abstract a hydride from the bisallylic methylene group at C3 of the cyclohexa-1,4-diene, thereby generating a high-energy Wheland intermediate, in other words, a strong Brønsted acid. The hydride and the proton are then both transferred to the acceptor in a stepwise process.

[Communication]
Indranil Chatterjee, Martin Oestreich
Angew. Chem. Int. Ed., December 21, 2014, DOI: 10.1002/anie.201409246. Read article.