Henry

Abstract

Transfers: Triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system. The work herein highlights the reductive transformations which lead to 1) C−N bond cleavage in N-benzyl and N-allylindoles and 2) reduction of polycyclic arenes to their dihydro derivatives.

[Communication]
Andrew J. Smith, Allan Young, Simon Rohrbach, Erin F. O'Connor, Mark Allison, Hong-Shuang Wang, Darren L. Poole, Tell Tuttle, John A. Murphy
Angew. Chem. Int. Ed., October 02, 2017, https://doi.org/10.1002/anie.201707914 Read article

Abstract

Nature Chemistry. doi:10.1038/nchem.2757

Authors: Teerawut Bootwicha, Julian M. Feilner, Eddie L. Myers & Varinder K. Aggarwal

Polypropionates can be grown — one carbon atom at a time — using the iterative homologation of boronic esters. This assembly line strategy was enabled through the use of enantioenriched lithiated α-chlorosilanes as masked carbinol units. Polypropionates were obtained in a fully stereocontrolled manner, including the stereochemically challenging anti–anti isomers.

Nature Chemistry. doi:10.1038/nchem.2748

Authors: Mattia Silvi, Charlie Verrier, Yannick P. Rey, Luca Buzzetti & Paolo Melchiorre

Chiral iminium ions generated from an amine catalyst and enals are key organocatalytic intermediates in thermal asymmetric processes. Now, visible-light excitation of these iminium ions can turn these compounds into strong oxidants to enable enantioselective photochemical β-alkylations of enals with silanes, which are unachievable via conventional ground state pathways.

Nature Chemistry. doi:10.1038/nchem.2723

Authors: Guoquan Liu, Marcel Levien, Niels Karschin, Giacomo Parigi, Claudio Luchinat & Marina Bennati

The analysis of complex (bio)molecules by NMR spectroscopy is often complicated by limitations in sensitivity. Now, it has been shown that 13C NMR signals are strongly enhanced in solution by resonant microwave irradiation of a nitroxide polarizer. This method exhibits up to 1,000-fold improvements in sensitivity, which stands to greatly improve the detail with which small molecules and metabolites can be studied.

Nature Chemistry. doi:10.1038/nchem.2735

Authors: David Lachkar, Natacha Denizot, Guillaume Bernadat, Kadiria Ahamada, Mehdi A. Beniddir, Vincent Dumontet, Jean-François Gallard, Régis Guillot, Karine Leblanc, Elvis Otogo N'nang, Victor Turpin, Cyrille Kouklovsky, Erwan Poupon, Laurent Evanno & Guillaume Vincent

The biomimetic syntheses of bipleiophylline, one of the most complex monoterpene indole alkaloids, and voacalgine A, its biosynthetic precursor, have been achieved from pleiocarpamine starting material. The development of a divergent oxidative coupling for the formation of the benzofuro[2,3-b]indolenine and isochromano[3,4-b]indolenine moieties was key to this accomplishment.