ChemInform Abstract: REACTION OF HALOFORMS WITH ADAMANTANE UNDER PHASE‐TRANSFER CATALYSIS CONDITIONS

Slobodin, Ya. M.; Ashkinazi, Leonid Aleksandrovich; Klimchuk, G. N.

doi:10.1002/chin.198448152

Cited by 2 publications

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“…While some cyclopropane rings activate adjacent C−H bonds, the cyclobutane ring in 52 obviously does not. In insertion reactions, the four-membered ring, therefore, behaves like the five-membered ring in dodecahedrane ( 3 ) 22 and the six-membered rings in adamantane, , where only insertion into the tertiary C−H bonds has been reported.…”

Section: Discussionmentioning

confidence: 99%

“…In contrast, intermolecular insertions of dihalocarbenes into nonactivated C−H bonds succeeded only with spheroidal molecules such as adamantane ( 1 ) , and dodecahedrane ( 3 ), where insertion exclusively occurred at the tertiary C−H bonds (Figure ). Moreover, insertion reactions of dichlorocarbene with a number of polycyclic hydrocarbons have been studied .…”

Section: Introductionmentioning

confidence: 99%

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Dihalocarbene Insertion Reactions into C−H Bonds of Compounds Containing Small Rings: Mechanisms and Regio- and Stereoselectivities^,

Brinker

Lin

et al. 2007

J. Org. Chem.

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Novel insertion reactions of dichloro- and dibromocarbene into carbon-hydrogen bonds adjacent to cyclopropane rings are reported. It is found that the predominant isomers formed in the reactions with bicyclo[4.1.0]heptane result from insertion into the endo carbon-hydrogen bonds alpha to the three-membered ring. In the reactions of bicyclo[3.1.0]hexane, however, the exo dihalocarbene insertion products are formed as the major isomers. In some compounds cyclopropane rings "activate" adjacent carbon-hydrogen bonds, whereas other systems containing three-membered rings do not. Moreover, the influence of various substituents (methyl, geminal dimethyl, phenyl, methoxy, and ethoxy) attached to bicyclo[3.1.0]hexane and bicyclo[4.1.0]heptane in dihalocarbene reactions has been studied. The findings can be explained by the concept of maximum orbital overlaps of Walsh orbitals of the cyclopropane rings and the alpha carbon-hydrogen bonds. In stark contrast, selective insertion into the tertiary carbon-hydrogen bonds of the cyclobutane ring in bicyclo[4.2.0]octane is observed.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Dihalocarbene Insertion Reactions into C−H Bonds of Compounds Containing Small Rings: Mechanisms and Regio- and Stereoselectivities^,

Brinker

Lin

et al. 2007

J. Org. Chem.

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“… a The hydride transfer potential (HTP) is obtained from the isodesmic equation CH 4 + R + → CH 3 + + RH by a single point energy calculation for the cation obtained by removal of a hydride ion from the optimized structure of the parent hydrocarbon. b In this experiment the Makosza PTC procedure was employed …”

Section: Resultsmentioning

confidence: 99%

Toward Selective Reactions with CH Bonds: A Rationale for the Regio- and Stereochemistry of Dichlorocarbene Insertions into Cyclic Hydrocarbons

Mieusset

Brinker

2007

J. Org. Chem.

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DFT calculations have been performed to study the course of dichlorocarbene insertion reactions into alkanes and to better understand the regio- and stereoselectivities observed. At the B3LYP/6-31G(d) level of theory, the selectivity of dichlorocarbene insertions into a number of hydrocarbons agrees well with the obtained experimental results. The reactivity of a specific C-H bond is determined by the capacity of the remaining alkyl fragment to effectively delocalize the partial positive charge buildup during the reaction. This activity can readily be estimated by calculation of the hydride transfer potential (HTP). A comparison with the structure and the stability of the corresponding cation is useful to emphasize the origins of the selectivity. Dichlorocarbene is also predicted to react efficiently with acidic C-H bonds through a nucleophilic-electrophilic mechanism. In principle, an attack of a carbene on an appropriately substituted three-membered ring may lead to fragmentation of the molecule.

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ChemInform Abstract: REACTION OF HALOFORMS WITH ADAMANTANE UNDER PHASE‐TRANSFER CATALYSIS CONDITIONS

Abstract: Adamantan (I) reagiert mit Haloformen unter den Bedingungen der Zweiphasenkatalyse nach dem kationoiden Mechanismus, wie durch Deuterierungsexperimente belegt wird.

Cited by 2 publications

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Dihalocarbene Insertion Reactions into C−H Bonds of Compounds Containing Small Rings: Mechanisms and Regio- and Stereoselectivities^,

Dihalocarbene Insertion Reactions into C−H Bonds of Compounds Containing Small Rings: Mechanisms and Regio- and Stereoselectivities^,

Toward Selective Reactions with CH Bonds: A Rationale for the Regio- and Stereochemistry of Dichlorocarbene Insertions into Cyclic Hydrocarbons

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ChemInform Abstract: REACTION OF HALOFORMS WITH ADAMANTANE UNDER PHASE‐TRANSFER CATALYSIS CONDITIONS

Abstract: Adamantan (I) reagiert mit Haloformen unter den Bedingungen der Zweiphasenkatalyse nach dem kationoiden Mechanismus, wie durch Deuterierungsexperimente belegt wird.

Cited by 2 publications

References 0 publications

Dihalocarbene Insertion Reactions into C−H Bonds of Compounds Containing Small Rings: Mechanisms and Regio- and Stereoselectivities,

Dihalocarbene Insertion Reactions into C−H Bonds of Compounds Containing Small Rings: Mechanisms and Regio- and Stereoselectivities,

Toward Selective Reactions with CH Bonds: A Rationale for the Regio- and Stereochemistry of Dichlorocarbene Insertions into Cyclic Hydrocarbons

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Dihalocarbene Insertion Reactions into C−H Bonds of Compounds Containing Small Rings: Mechanisms and Regio- and Stereoselectivities^,

Dihalocarbene Insertion Reactions into C−H Bonds of Compounds Containing Small Rings: Mechanisms and Regio- and Stereoselectivities^,