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A Supramolecular Chiral Auxiliary Approach: “Remote Control” of Stereochemistry at a Hierarchically Assembled Dimeric Helicate
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David Van Craen Prof. Dr. Markus Albrecht Prof. Dr. Gerhard Raabe Fangfang Pan Prof. Dr. Kari Rissanen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3255-3258
Dimeric hierarchically‐assembled titanium(IV) helicates are in solvent‐dependent equilibrium with the corresponding monomers. Statistically formed mixtures of such complexes bearing chiral stereocontrolling ligands and achiral diene‐substituted ligands show high diastereoselectivity and reasonable enantioselectivity in the Diels–Alder reaction with maleimides if the reaction proceeds with the dimer but not with the monomer. Thus, solvent dependent switching between the monomer and dimer enables on/off switching of the enantioselectivity. 相似文献
198.
The new adduct W4Br10 · 2SbBr3 and the new binary compound W4Br10 were obtained as products in a reaction cascade in which WBr6 was reacted with elemental antimony at successively increased temperatures. The crystal structures of both compounds were refined from X‐ray powder diffraction data and their electronic structures were analyzed by MO calculations. The cluster compounds W4Br10 · 2SbBr3 and W4Br10 appear as intermediates in the solid state nucleation of W6Br12. The overall reaction cascade involves tungsten clusters having tetrahedral (W4), square pyramidal (W5) and finally octahedral (W6) cluster cores. 相似文献
199.
Thomas Weymuth Moritz P. Haag Karin Kiewisch Sandra Luber Stephan Schenk Christoph R. Jacob Carmen Herrmann Johannes Neugebauer Markus Reiher 《Journal of computational chemistry》2012,33(27):2186-2198
We present the software package MO VI PAC for calculations of vibrational spectra, namely infrared, Raman, and Raman Optical Activity (ROA) spectra, in a massively parallelized fashion. MO VI PAC unites the latest versions of the programs SNF and AKIRA alongside with a range of helpful add‐ons to analyze and interpret the data obtained in the calculations. With its efficient parallelization and meta‐program design, MO VI PAC focuses in particular on the calculation of vibrational spectra of very large molecules containing on the order of a hundred atoms. For this purpose, it also offers different subsystem approaches such as Mode‐ and Intensity‐Tracking to selectively calculate specific features of the full spectrum. Furthermore, an approximation to the entire spectrum can be obtained using the Cartesian Tensor Transfer Method. We illustrate these capabilities using the example of a large π‐helix consisting of 20 (S)‐alanine residues. In particular, we investigate the ROA spectrum of this structure and compare it to the spectra of α‐ and 310‐helical analogs. © 2012 Wiley Periodicals, Inc. 相似文献
200.
Generation of an N→B Ladder‐type Structure by Regioselective Hydroboration of an Alkenyl‐Functionalized Quaterpyridine
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Markus Grandl Dr. Yu Sun Dr. Frank Pammer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(12):3976-3980
An unusual reactivity of 2‐(1‐alkenyl)‐pyridines towards hydroboration with 9H‐borabicyclo[3.3.1]nonane (9H‐BBN) has been employed to selectively introduce two borane groups into a conjugated quaterpyridine. Quantitative conversion of the substrate was observed with exclusive regioselectivity. A molecular structure that allows intramolecular N→B coordination was generated. The effect of the ladder formation on the molecular structure and the electronic properties of the conjugated system have been investigated. The synthetic strategy demonstrated herein offers a facile access to N→B ladder‐type structures from readily available substrates, and allows to simultaneously introduce several boron centers under mild conditions. 相似文献