1998
DOI: 10.1021/ja981272t
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Catalytic CN Bond Formation by Metal-Imide-Mediated Imine Metathesis

Abstract: Molybdenum bis(imide) complexes of the general formula (DME)Cl2Mo(NR)2 catalytically metathesize acyclic imine substrates. This CN bond-forming reaction has significant implications for the synthesis of small molecules by ring-closing metathesis and polymers by ring-opening metathesis. A series of closely related NR transfer reactions were examined in an effort to fully understand the process. (RO)2Mo(CHR‘)(NAr) (1a, Ar = 2,6-diisopropylphenyl in all cases; R = C(CF3)2CH3) underwent alkylidene/imine excha… Show more

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Cited by 96 publications
(62 citation statements)
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“…Evidently, the key bond lengths and angles of 5 a are remarkably similar to those of complexes 15 and 16. Although the C ± N bond lengths (d 2 and d 3 ) in 5 a are different owing to the lack of p-bond delocalization; their average value is almost identical to the CÀN bond lengths in 15 and 16. These observations should be important as they shed light on the relative contribution of the M 3 Py backbonding to the overall M ± Py axial ligation in bis(pyridine)metalloporphyrins.…”
Section: Resultsmentioning
confidence: 91%
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“…Evidently, the key bond lengths and angles of 5 a are remarkably similar to those of complexes 15 and 16. Although the C ± N bond lengths (d 2 and d 3 ) in 5 a are different owing to the lack of p-bond delocalization; their average value is almost identical to the CÀN bond lengths in 15 and 16. These observations should be important as they shed light on the relative contribution of the M 3 Py backbonding to the overall M ± Py axial ligation in bis(pyridine)metalloporphyrins.…”
Section: Resultsmentioning
confidence: 91%
“…Metal complexes with simple imine (N(R'')CRR') or methyleneamido (NCRR', an alternative and common term: azavinylidene) groups, where R H, alkyl/aryl, have been observed or proposed to be key intermediates in a number of metal-mediated processes, such as interconversion between amines and nitriles, [1] aziridination of imine by a carbene donor, [2] imine, alkylidene/imine, imide/imine metatheses, [3] and N-arylation of imines [4] (Reactions a ± f in Scheme 1). Investigations into the interaction between a metalloporphyrin and a simple imine or methyleneamido group would be of fundamental interest for the application of metalloporphyrins to these processes, which should be attractive because metalloporphyrins that function as catalysts often feature high activity and selectivity [5] and are robust if there are appropriate substituents on the porphyrin rings.…”
Section: Introductionmentioning
confidence: 99%
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“…Finally, the reaction of 1b-III with aldehyde 2a leads to bicycle 4a via the iminium ion 1b-V. Scheme Thiazolidines are imino-type compounds, having the ability to exchange at the acetalic position with different aldehydes. [8][9][10][11] Imine exchange is a process triggered by acid catalysis, [12] amine [13,14] or transition metal complexes containing a metal-imido group M=NR (M = Zr, [15] Mo, [16] Nb, [17] Ti, [18] Hf [19] ). We envisioned the potentiality of this phenomenon in bisthiazolidines as well.…”
Section: Introductionmentioning
confidence: 99%
“…Similar to imine formation, transimination also proceeds to the formation of tetrahedral intermediate (aminal) that subsequently decomposes to give a new imine and amine. [10][11][12][13][14][15][16] Recently, Stefano and Ciaccia critically discussed the mechanism operating in imine chemistry in organic solvents and unambiguously explained the mechanistic aspects of hydrolysis, transimination, and metathesis reactions. 3 Transimination may be homotransimination (both amines are aliphatic or aromatic) and heterotransimination (one is aliphatic and other is aromatic) and influence by Brönsted and Lewis acids, [4][5][6] for instance, Sc III triflate salts catalyse the exchange reactions between sterically hindered imines, derived from 9anthracenecarboxaldehyde, and several amines in chloroform.…”
Section: Introductionmentioning
confidence: 99%