Anti-selective catalytic asymmetric nitroaldol reaction via a heterobimetallic heterogeneous catalyst

Tatsuya Nitabaru, Akihiro Nojiri, Makoto Kobayashi, Naoya Kumagai, Masakatsu Shibasaki

Research output: Contribution to journalArticlepeer-review

121 Citations (Scopus)

Abstract

Full details of an anti-selective catalytic asymmetric nitroaldol reaction promoted by a heterobimetallic catalyst comprised of Nd5O(O iPr)13, an amide-based ligand, and NaHMDS (sodium hexamethyldisilazide) are described. A systematic synthesis and evaluation of amide-based ligands led to the identification of optimum ligand 1m, which provided a suitable platform for the Nd/Na heterobimetallic complex. During the catalyst preparation in THF, a heterogeneous mixture developed and centrifugation of the suspension allowed for separation of the precipitate, which contained the active catalyst and which could be stored for at least 1 month without any loss of catalytic performance. The precipitate promoted a nitroaldol (Henry) reaction for a broad range of nitroalkanes and aldehydes under heterogeneous conditions, affording the corresponding 1,2-nitroalkanol in a highly anti-selective (up to anti/syn = >40/1) and enantioselective manner (up to 98% ee). Inductively coupled plasma (ICP) and X-ray fluorescence (XRF) analyses revealed that the precipitate indeed included both neodymium and sodium, which was further supported by high-resolution ESI TOF MS spectrometry.

Original languageEnglish
Pages (from-to)13860-13869
Number of pages10
JournalJournal of the American Chemical Society
Volume131
Issue number38
DOIs
Publication statusPublished - 2009
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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