Toward Asymmetric Synthesis of Pentaorganosilicates

Leon J.P. van der Boon, Shin ichi Fuku-en, J. Chris Slootweg, Koop Lammertsma, Andreas W. Ehlers

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Introducing chiral silicon centers was explored for the asymmetric Rh-catalyzed cyclization of dihydrosilanes to enantiomerically enriched spirosilanes as targets to enable access to enantiostable pentacoordinate silicates. The steric rigidity required in such systems demands the presence of two naphthyl or benzo[b]thiophene groups. The synthetic approach to the expanded spirosilanes extends Takai’s method (Kuninobu et al. in Angew Chem Int Ed 52(5):1520–1522, 2013) for the synthesis of spirosilabifluorenes in which both a Si–H and a C–H bond of a dihydrosilane are activated by a rhodium catalyst. The expanded dihydrosilanes were obtained from halogenated aromatic precursors. Their asymmetric cyclization to the spirosilanes were conducted with [Rh(cod)Cl]2 in the presence of the chiral bidentate phosphane ligands (R)-BINAP, (R)-MeO-BIPHEP, and (R)-SEGPHOS, including derivatives with P-(3,5-t-Bu-4-MeO)-phenyl (DTBM) groups. The highest enantiomeric excess of 84% was obtained for 11,11′-spirobi[benzo[b]-naphtho[2,1-d]silole] with the DTBM-SEGPHOS ligand.

Original languageEnglish
Pages (from-to)674-684
Number of pages11
JournalTopics in Catalysis
Volume61
Issue number7-8
Early online date20 Apr 2018
DOIs
Publication statusPublished - Jun 2018

Fingerprint

phosphine
Cyclization
Ligands
Silicates
Rhodium
Thiophene
Silicon
Rigidity
Derivatives
Catalysts
2-naphthol BINAP
silole
benzothiophene

Keywords

  • Asymmetric catalysis
  • Silicates
  • Spirosilanes

Cite this

van der Boon, Leon J.P. ; Fuku-en, Shin ichi ; Slootweg, J. Chris ; Lammertsma, Koop ; Ehlers, Andreas W. / Toward Asymmetric Synthesis of Pentaorganosilicates. In: Topics in Catalysis. 2018 ; Vol. 61, No. 7-8. pp. 674-684.
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Toward Asymmetric Synthesis of Pentaorganosilicates. / van der Boon, Leon J.P.; Fuku-en, Shin ichi; Slootweg, J. Chris; Lammertsma, Koop; Ehlers, Andreas W.

In: Topics in Catalysis, Vol. 61, No. 7-8, 06.2018, p. 674-684.

Research output: Contribution to JournalArticleAcademicpeer-review

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