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11.
The aziridinium ylide generated by the intramolecular reaction of a metal carbenoid tethered to a vinylaziridine undergoes [2,3]-Stevens rearrangement to furnish the indolizidine skeleton. It is essential that the correct nitrogen invertomer is used or a competing [1,5]-hydrogen shift predominates. During the preparation of a second system a `one-pot' acylation-[3,3]-Claisen rearrangement was observed, delivering a seven-membered lactam.  相似文献   
12.
The benzoin reaction, catalyzed by simple 1-N-alkyl-3-methylimidazolium salt-based ionic liquid via carbene intermediate, to give the α-hydroxyl ketone proceeds in CH2Cl2 under mild conditions.  相似文献   
13.
Rongti Li 《Tetrahedron letters》2005,46(31):5117-5120
Coupling of alkynylbenzoyl systems with γ,δ-unsaturated Fischer carbene complexes leads to the formation of hydrophenanthrene derivatives. This reaction is not affected by aqueous systems, which offer a further advantage such that chromium hexacarbonyl sublimes during the reaction process. Chromium carbene-alkyne coupling processes can thus be performed in environmentally friendly solvents with substoichiometric net consumption of chromium hexacarbonyl.  相似文献   
14.
Dibromocarbene reacts with tertiary-butylisocyanide to form a ketenimine. The absolute rate constant of the reaction (kTBI = 2.3 × 109 M−1 s−1) was determined by laser flash photolysis techniques with UV-vis detection of the dibromocarbene-pyridine ylide. The ketenimine was detected by TRIR spectroscopy at 2040 cm−1. Isocyanide trapping of carbenes to form ketenimines is proposed as a general method of studying IR silent carbenes by TRIR spectroscopy.  相似文献   
15.
Fischer carbene complexes 1 underwent a clean ligand dimerization reaction yielding functionalized olefins and trienes 4 in the presence of copper (I) catalysts. If treated with trifluoroacetic acid (TFA), trienes 4c, d, f undergo a cyclization process (Nazarov reaction) which furnishes cyclopentenone derivatives 6c, d, 7c, d and 8 in good yields. Finally, the Fischer aminocarbene 9 efficiently cyclodimerizes to the substituted arene 10 in the presence of CuBr.  相似文献   
16.
Michael Klein 《Tetrahedron》2004,60(5):1087-1092
The synthesis of an enediyne sulfonamide by alkylidene carbene rearrangement is reported. The compound cyclizes thermally to give the Bergman product, which was prepared independently for comparison. Like other σ-acceptor substituents at the enediyne alkyne termini, such as fluoride, oxonium or ammonium groups, the sulfonamide moiety enhances the reactivity for thermal Bergman cyclization as shown by the cyclization kinetic of the title compound.  相似文献   
17.
A new ferrocenyl-N-heterocyclic carbene ligand precursor 1,1′-bis[(1-tert-butylimidazolium)-3-methyl]ferrocene dichloride has been synthesised and structurally characterised. The imidazolium salt was readily deprotonated in situ with KN(SiMe3)2 and reacted with [PdCl2 (cod)] to afford the structurally characterised palladium (II) complex trans-[PdCl2(CfcC)], where (cod) = 1,5-cyclooctadiene and (CfcC) = 1,1′-di-tert-butyl-3,3′-(1,1′-dimethyleneferrocenyl)-diimidazol-2-ylidene.  相似文献   
18.
Alkyl substituted chromium Fischer carbene complexes react with 1,1-diphenylallene in the presence of rhodium(I) catalysts (10 mol%) to yield highly substituted dienyl indenone derivatives. In this process a catalytic chromium(0)-rhodium(I) exchange occurs, four new C-C bonds are created, and four-components (two allenes, the carbene ligand and one CO ligand) are joined in a chemo- and regioselective manner.  相似文献   
19.
20.
The reaction of N-fluoropyridinium triflate with isonitriles in acetonitrile and propionitrile in the presence of NaBH(OAc)3 led to the formation of the corresponding imidazo[1,2-a]pyridines in 44-73% yields. The proposed reaction mechanism involves the intermediate formation of a highly reactive carbene species and apparent reduction of the pyridinium intermediate with NaBH(OAc)3 to yield the targeted heterocycles.  相似文献   
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