3 research outputs found
β‑H Abstraction/1,3‑CH Bond Addition as a Mechanism for the Activation of CH Bonds at Early Transition Metal Centers
This
article describes the generalization of an overlooked mechanism
for CH bond activation at early transition metal centers, namely 1,3‑CH
bond addition at an η<sup>2</sup>-alkene intermediate. The X-ray-characterized
[Cp<sub>2</sub>Zr(<i>c</i>-C<sub>3</sub>H<sub>5</sub>)<sub>2</sub>] eliminates cyclopropane by a β‑H abstraction
reaction to generate the transient η<sup>2</sup>-cyclopropene
[Cp<sub>2</sub>Zr(η<sup>2</sup>-<i>c</i>-C<sub>3</sub>H<sub>4</sub>)] intermediate <b>A</b>. <b>A</b> rapidly
cleaves the CH bond of furan and thiophene to give the furyl and thienyl
complexes [Cp<sub>2</sub>Zr(<i>c</i>-C<sub>3</sub>H<sub>5</sub>)(2-C<sub>4</sub>H<sub>3</sub>X)] (X = O, S), respectively.
Benzene is less cleanly activated. Mechanistic investigations including
kinetic studies, isotope labeling, and DFT computation of the reaction
profile all confirm that rapid stereospecific 1,3‑CH
bond addition across the Zr(η<sup>2</sup>-alkene) bond of <b>A</b> follows the rate-determining β‑H abstraction
reaction. DFT computations also suggest that an α‑CC
agostic rotamer of [Cp<sub>2</sub>Zr(<i>c</i>-C<sub>3</sub>H<sub>5</sub>)<sub>2</sub>] assists the β‑H abstraction
of cyclopropane. The nature of the α‑CC agostic
interaction is discussed in the light of an NBO analysis
β‑H Abstraction/1,3‑CH Bond Addition as a Mechanism for the Activation of CH Bonds at Early Transition Metal Centers
This
article describes the generalization of an overlooked mechanism
for CH bond activation at early transition metal centers, namely 1,3‑CH
bond addition at an η<sup>2</sup>-alkene intermediate. The X-ray-characterized
[Cp<sub>2</sub>Zr(<i>c</i>-C<sub>3</sub>H<sub>5</sub>)<sub>2</sub>] eliminates cyclopropane by a β‑H abstraction
reaction to generate the transient η<sup>2</sup>-cyclopropene
[Cp<sub>2</sub>Zr(η<sup>2</sup>-<i>c</i>-C<sub>3</sub>H<sub>4</sub>)] intermediate <b>A</b>. <b>A</b> rapidly
cleaves the CH bond of furan and thiophene to give the furyl and thienyl
complexes [Cp<sub>2</sub>Zr(<i>c</i>-C<sub>3</sub>H<sub>5</sub>)(2-C<sub>4</sub>H<sub>3</sub>X)] (X = O, S), respectively.
Benzene is less cleanly activated. Mechanistic investigations including
kinetic studies, isotope labeling, and DFT computation of the reaction
profile all confirm that rapid stereospecific 1,3‑CH
bond addition across the Zr(η<sup>2</sup>-alkene) bond of <b>A</b> follows the rate-determining β‑H abstraction
reaction. DFT computations also suggest that an α‑CC
agostic rotamer of [Cp<sub>2</sub>Zr(<i>c</i>-C<sub>3</sub>H<sub>5</sub>)<sub>2</sub>] assists the β‑H abstraction
of cyclopropane. The nature of the α‑CC agostic
interaction is discussed in the light of an NBO analysis
Chemo‑, Regio‑, and Stereoselective Silver-Catalyzed Aziridination of Dienes: Scope, Mechanistic Studies, and Ring-Opening Reactions
Silver
complexes bearing trispyrazolylborate ligands (Tp<sup>x</sup>) catalyze
the aziridination of 2,4-diene-1-ols in a chemo-, regio-,
and stereoselective manner to give vinylaziridines in high yields
by means of the metal-mediated transfer of NTs (Ts = <i>p</i>-toluensulfonyl) units from PhINTs. The preferential aziridination
occurs at the double bond neighboring to the hydroxyl end in ca. 9:1
ratios that assessed a very high degree of regioselectivity. The reaction
with the silver-based catalysts proceeds in a stereospecific manner,
i.e., the initial configuration of the CC bond is maintained
in the aziridine product (<i>cis</i> or <i>trans</i>). The degree of regioselectivity
was explained with the aid of DFT studies, where the directing effect
of the OH group of 2,4-diene-1-ols plays a key role. Effective
strategies for ring-opening of the new aziridines, deprotection of
the Ts group, and subsequent formation of β-amino alcohols have
also been developed