Cyclopropanes from reactions of transition metal carbene complexes with olefins

Brookhart, Maurice; Studabaker, William B.

doi:10.1021/cr00078a008

Cited by 401 publications

(205 citation statements)

References 14 publications

(24 reference statements)

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“…10,11 A review Cyclopropanes from Reactions of Transition-Metal-Carbene Complexes with Olefins has appeared. 12 Complexes 3 are generated in situ from isolable precursors 1 9 or 2 11 through O-and S-methylation and elimination of the respective (thio-)ether. The triphenylphosphine substituted complexes 3a were sufficiently stable to be characterized by 1 H and 13 C NMR.…”

Section: A [2+1] Metal-assisted Cycloaddition Reactionsmentioning

confidence: 99%

“…28 The cyclopropanation of olefins by Fischer carbene complexes has been addressed in several reviews and monographs. 6,12,[29][30][31][32][33] In the early 1970s Fischer and co-workers [34][35][36][37][38] reported on the first carbene transfer reactions of (phenylmethoxycarbene)pentacarbonylchromium (4). It became apparent that the cyclopropanation of olefins did not involve a free carbene.…”

Section: A [2+1] Metal-assisted Cycloaddition Reactionsmentioning

confidence: 99%

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Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

1997

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Section: A [2+1] Metal-assisted Cycloaddition Reactionsmentioning

confidence: 99%

Section: A [2+1] Metal-assisted Cycloaddition Reactionsmentioning

confidence: 99%

Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

1997

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“…How structural factors (bond angle, electron-withdrawal by induction and electron-donation by resonance) influence the relative stabilities of these states is still under scrutiny [1]. The synthetic organic chemistry [2], organometallic chemistry [3] and other areas, principally; the ArndtEistert chain homologation procedure, the Rimer-Tiemann reaction (formylation of phenols), cyclopropanation of alkenes [4] and subsequent rearrangements, [5] ketene and allene [6] preparation, synthesis of strained ring systems, ylide generation and subsequent rearrangements, cycloaddition reactions [7] and photoaffinity labeling. [8] are some of the vital fields of wide applications of the carbenes and halocarbenes…”

Section: Introductionmentioning

confidence: 99%

Ab Initio and DFT Investigations of the Mechanistic Pathway of Singlet Bromocarbenes Insertion into C-H Bonds of Methane and Ethane

Ramalingam

Ramasami²,

Venuvanalingam

et al. 2007

Computational Science – ICCS 2007

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Abstract. The mechanistic pathway of singlet bromocarbenes ( 1 CHBr and 1 CBr 2 ) insertions into the C-H bonds of methane and ethane have been analysed at ab initio (HF and MP2) and DFT (B3LYP) level of theories using 6-31g (d, p) basis set. The QCISD//MP2/6-31g(d, p) level predicts higher activation barriers. NPA, Mulliken and ESP charge analyses have been carried out along the minimal reaction path by the IRC method at B3LYP and MP2 levels for these reactions. The occurrence of the TSs either in the electrophilic or nucleophilic phase and net charge flow from alkane to carbene in the TS has been identified through NBO analyses.

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“…A number of metal complexes are able to catalyze the transfer of carbene from diazo compounds to alkene through metal-carbene complexes [4,5]. Homogeneous rhodium-and copperbased catalysts have been extensively studied and some systems could achieve selectively and yield higher than 90% in cyclopropanes [6][7][8]. For hetero-geneous systems, copper-bronze has been the only popular catalyst for this reaction since it was first found several decades ago [9].…”

Section: Introductionmentioning

confidence: 99%