Synthesis of α,α-disubstituted acetic acids using low-valent titanium

García, María del Pilar; Campo, Carlos; Llama, E. F.; Sinisterra, J. V.

doi:10.1039/p19950001771

Cited by 21 publications

(9 citation statements)

References 35 publications

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“…It is well known that carbene plays an important role in organic chemistry, especially for the addition reaction with the C=C and C=O double bonds [1][2][3][4]. Therefore, the studies of carben have attracted more attentions theoretically and experimentally.…”

Section: Introductionmentioning

confidence: 99%

Insights into the reaction mechanism between propadienylidene and ethylene: a DFT study

Tan

Liu

et al. 2011

Struct Chem

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The reaction mechanism between propadienylidene and ethylene has been systematically investigated employing the B3LYP/6-311??G** and MP2/cc-pVTZ levels of theory to better understand the reactivity of propadienylidene with unsaturated hydrocarbons. Geometry optimization, vibrational analysis, and energy property for the involved stationary points on the potential energy surface have been calculated. Two important initial reaction complexes characterized by three-and four-membered ring structures have been located firstly. After that, three different products possessing three-, four-, and five-membered ring characters have been obtained through three reaction pathways. In the first reaction pathway, a threemembered ring alkyne compound has been obtained. As for the second reaction pathway, it is a diffusion-controlled reaction, resulting in the formation of the four-membered ring conjugated diene compound. A five-membered conjugated diene compound has been obtained in the third reaction pathway, which is the most stable product in the available products thermodynamically. On the other hand, the second reaction pathway is the most favorable reaction to proceed kinetically.

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Section: Introductionmentioning

confidence: 99%

Insights into the reaction mechanism between propadienylidene and ethylene: a DFT study

Tan

Liu

et al. 2011

Struct Chem

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“…Carbenes play an important role in organic chemistry, especially for the addition reaction between carbene and C=O double bond [1][2][3][4]. Therefore, they have attracted much attention not only from theoretical but also applied chemists.…”

Section: Introductionmentioning

confidence: 99%

A theoretical study on the mechanism of the addition reaction between carbene and epoxyethane

Tan

Zheng

et al. 2009

Struct Chem

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The mechanism of addition reaction between carbene and epoxyethane has been investigated employing the MP2 and B3LYP/6-311?G* levels of theory. Geometry optimization, vibrational analysis, and energy property for the involved stationary points on the potential energy surface have been calculated. Based on the calculated results at the MP2/6-311?G* level of theory, it can be predicted that there are two reaction mechanisms (1) and (2). In the first reaction carbene attacks the atom O of epoxyethane to form an intermediate 1a (IM1a), which is a barrier-free exothermic reaction. Then, IM1a can isomerize to IM1b via a transition state 1a (TS1a), where the potential barrier is 48.6 kJ/mol. Subsequently, IM1b isomerizes to a product epoxypropane (Pro1) via TS1b with a potential barrier of 14.2 kJ/mol. In the second carbene attacks the atom C of epoxyethane firstly to form IM2 via TS2a. Then IM2 isomerizes to a product allyl alcohol (Pro2) via TS2b with a potential barrier of 101.6 kJ/mol. Correspondingly, the reaction energies for the reactions (1) and (2) are -448.4 and -501.6 kJ/mol, respectively. Additionally, the orbital interactions are also discussed for the leading intermediate. The results based on the B3LYP/6-311?G* level of theory are paralleled to those on the MP2/6-311?G* level of theory. Furthermore, the halogen and methyl substituent effects of H 2 C: on the two reaction mechanisms have been investigated. The calculated results indicate that the introductions of halogen or methyl make the addition reaction difficult to proceed.

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“…It is well known that carbene plays an important role in organic chemistry, especially for the addition reaction with C=C and C=O double bond. [1][2][3][4] Therefore, the studies of carbene have attracted more attentions theoretically and experimentally. For example, carbene can be used to provide simple and direct synthesis for small-ring, highly strained compounds, as well as those that are hardly synthesized through conventional ways.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on the Mechanism of the Addition Reaction between Cyclopropenylidene and Formaldehyde

Tan¹,

Li²,

Sun³

et al. 2012

Bulletin of the Korean Chemical Society

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Synthesis of α,α-disubstituted acetic acids using low-valent titanium

Cited by 21 publications

References 35 publications

Insights into the reaction mechanism between propadienylidene and ethylene: a DFT study

Insights into the reaction mechanism between propadienylidene and ethylene: a DFT study

A theoretical study on the mechanism of the addition reaction between carbene and epoxyethane

Theoretical Study on the Mechanism of the Addition Reaction between Cyclopropenylidene and Formaldehyde

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