Undeniable Confirmation of the syn-Addition Mechanism for Metal-Free Diboration by Using the Crystalline Sponge Method

Ana B. Cuenca, Nicolas Zigon, Vincent Duplan, Manabu Hoshino, Makoto Fujita, Elena Fernández

Research output: Indexed journal article Articlepeer-review

49 Citations (Scopus)

Abstract

The stereochemical outcome of the recently developed metal-free 1,2-diboration of aliphatic alkenes has, until now, only been elucidated by indirect means (e.g. derivatization). This is because classical conformational analysis of the resulting 1,2-diboranes is not viable; in the 1H NMR spectrum the relevant 1H resonances are broadened by 11B, and the occurrence of the products as oily compounds precludes X-ray crystallographic analysis. Herein, the crystalline sponge method is used to display the crystal structures of the diboronic esters formed from internal E and Z olefins, evidencing the stereospecific syn addition mechanism of the reaction, which is fully consistent with the prediction from DFT calculations. The crystalline sponge method provides conclusive proof of the stereospecific addition in the metal-free diboration of internal aliphatic alkenes (see scheme). The compatibility of common boryl groups with a monoporous ZnI2 network gives access to the crystal structures of the oily organoborane compounds. The relative stereochemistry of the metal-free diboration products was unequivocally assigned and fully consistent with the DFT calculations.

Original languageEnglish
Pages (from-to)4723-4726
Number of pages4
JournalChemistry - A European Journal
Volume22
Issue number14
DOIs
Publication statusPublished - 24 Mar 2016
Externally publishedYes

Keywords

  • 1 2-diboron
  • configuration
  • crystalline sponge method
  • diboron inclusion
  • organocatalysis

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