Reactions of methylphenylcarbene and phenylcarbene in isobutene matrices: origins of the "insertion" products

Moss, Robert A.; Joyce, Martin

doi:10.1021/ja00446a047

Cited by 21 publications

(2 citation statements)

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“…We have shown recently that a neopentylidene complex, TaCp(CHCMe3)Cl2, reacts with ethylene to give 4,4-dimethyl-1-pentene,1 probably by transfer of a /3-hydrogen atom selectively to the substituted -carbon atom in an intermediate tantallocyclobutane complex.2 If the organometallic product of the initial reaction, CpChTaCTUCH^CH^iHa (1), were to decompose similarly,3 it would be a catalyst for dimerizing ethylene selectively to 1-butene, an almost unknown result for metal hydride based homogeneous catalysts. 4 We present re-©…”

Section: Sirmentioning

confidence: 98%

Reactions of carbenes at low temperatures. Diphenylcarbene and isobutene

Moss¹,

Huselton²

1978

J. Am. Chem. Soc.

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Section: Sirmentioning

confidence: 98%

Reactions of carbenes at low temperatures. Diphenylcarbene and isobutene

Moss¹,

Huselton²

1978

J. Am. Chem. Soc.

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“…In the case of diphenyldiazomethane [113] and methyphenyldiazomethane, [133] pure triplet carbene chemistry in olefinic matrices was observed, since cyclopropane rings are formed after decay of the singlet carbene to triplet ground state at low temperatures. An abstraction-recombination mechanism was attributed to be in the basis of cyclopropane formation.…”

Section: Tbmpmentioning

confidence: 99%

Developments in the Photochemistry of Diazo Compounds

Candeias¹,

Afonso

2009

COC

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This review focus on photolytic reactions of diazo compounds, covering mainly synthetic applications such as Wolff rearrangement, 1,2-shift, X-H insertion, cyclopropanation, hydrogen abstraction and reaction with oxygen and physical organic studies, with special relevance to mechanistic considerations. the synthesis of a diazo compound if loss of a proton from the C()-atom of the primarily formed alkanediazonium ion is faster than the loss of dinitrogen, which makes this method almost specific for the case of aliphatic amines containing a C()-atom substituted by an acidifying group. Diazo compounds can also be prepared by acylation or cleavage of aliphatic diazo compounds containing the structural requirements. For instance, diazo carbonyl carbamate 4 can be prepared through the reaction of the carboxylate precursor with a chloroformate and further reaction of the anhydride with diazomethane (Scheme 2).[13] Making use of oxidants, diazo carbonyl compounds can be prepared by hydrazone oxidation in the presence of mercury oxide and potassium hydroxide.[14] Scheme 1 Scheme 2 Diazo-transfer reactions have been widely used since they are a more general method for the preparation of diazo compounds. In this reaction, the diazo moiety is transferred from the donor to an acceptor where the donor is a sulphonyl azide (6) and the acceptor a carbanion formed after deprotonation (Scheme 3).[3,15] Scheme 3 Diazo compounds can be submitted to several reaction conditions and myriads of compounds can be obtained by the proper choice of conditions and reagents. In the absence of a metal catalyst, this decomposition can be induced by thermolysis or photolysis, generating a highly reactive intermediate species that, in most cases, affords a complex mixture of products. Depending on the diazo compound and the reaction conditions, the resulting products can be derived from C-H or X-H

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