Herstellung von β-Hydroxyestern aus Carbonyl-Verbindungen und Keten in Gegenwart von Titan-alkoxiden

Vuitel, L.; Jacot‐Guillarmod, André

doi:10.1055/s-1972-21947

Cited by 17 publications

(2 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Insertion of the CC or CO bond of a ketene into the Ti−O or M−N bond has been documented . It is interesting to know how a ketene reacts with 3a , as it contains both Ti−O and Ti−N bonds.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structure, and Reactivity of [σ:η¹:η⁵-(OCH₂)(Me₂NCH₂)C₂B₉H₉]Ti(NR₂) (R = Me, Et)

2007

View full text Add to dashboard Cite

Interaction of [Me3NH][7,8-CH2OCH2-7,8-C2B9H10] with M(NR2)4 gave the simple amine elimination products [η5-(CH2OCH2)C2B9H9]M(NMe2)2(NHMe2) (M = Zr (2a), Hf (2b)) or the unexpected C−O bond cleavage products [σ:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti(NR2) (R = Me (3a), Et (3b)). The higher oxophilicity of the Ti center provides the driving force for the latter reactions. It is suggested that the C−O bond cleavage is prior to the amine elimination in the formation of 3a,b. This serves as a convenient and practical method for the preparation of constrained-geometry half-sandwich metallacarboranes with two different functional sidearms. Complex 3a can undergo a clean amine exchange reaction to produce new constrained-geometry titanacarborane amides. Reactions of 3a with unsaturated molecules CyNCNCy, SCS, Xyl−NC, PhC⋮N, Bu n NCS, Ph2CCO, and PhNCO gave monoinsertion products. They, except for [σ:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti[η3-CyNC(NMe2)NCy] (7), do not react with amines. In sharp contrast, 7 can react readily with Me2NH to regenerate 3a and release guanidine, which leads to the discovery of new catalytic guanylation of amines. All new complexes were fully characterized by various spectroscopic techniques and elemental analyses. Most of them were further confirmed by single-crystal X-ray analyses.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis, Structure, and Reactivity of [σ:η¹:η⁵-(OCH₂)(Me₂NCH₂)C₂B₉H₉]Ti(NR₂) (R = Me, Et)

2007

View full text Add to dashboard Cite

show abstract

“…Insertion of the C@C or C@O bond of a ketene into the Ti-O or M-N bond has been documented [41][42][43][44]. In the present case, only C@O insertion product [r:g 1 :g 5 -(OCH 2 )(Me 2 NCH 2 )C 2 B 9 H 9 ]-Ti[r:g 1 -OC(NMe 2 )@CPh 2 ] was isolated.…”

Section: Insertion Reactionmentioning

confidence: 50%

Titanacarborane mediated C–N bond forming/breaking reactions

Shen

Xie

2009

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

Preparation of Difunctional Compounds

1974

Compendium of Organic Synthetic Methods

View full text Add to dashboard Cite

Herstellung von β-Hydroxyestern aus Carbonyl-Verbindungen und Keten in Gegenwart von Titan-alkoxiden

Cited by 17 publications

References 0 publications

Synthesis, Structure, and Reactivity of [σ:η¹:η⁵-(OCH₂)(Me₂NCH₂)C₂B₉H₉]Ti(NR₂) (R = Me, Et)

Synthesis, Structure, and Reactivity of [σ:η¹:η⁵-(OCH₂)(Me₂NCH₂)C₂B₉H₉]Ti(NR₂) (R = Me, Et)

Titanacarborane mediated C–N bond forming/breaking reactions

Preparation of Difunctional Compounds

Contact Info

Product

Resources

About

Herstellung von β-Hydroxyestern aus Carbonyl-Verbindungen und Keten in Gegenwart von Titan-alkoxiden

Cited by 17 publications

References 0 publications

Synthesis, Structure, and Reactivity of [σ:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti(NR2) (R = Me, Et)

Synthesis, Structure, and Reactivity of [σ:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti(NR2) (R = Me, Et)

Titanacarborane mediated C–N bond forming/breaking reactions

Preparation of Difunctional Compounds

Contact Info

Product

Resources

About

Synthesis, Structure, and Reactivity of [σ:η¹:η⁵-(OCH₂)(Me₂NCH₂)C₂B₉H₉]Ti(NR₂) (R = Me, Et)

Synthesis, Structure, and Reactivity of [σ:η¹:η⁵-(OCH₂)(Me₂NCH₂)C₂B₉H₉]Ti(NR₂) (R = Me, Et)