|
| ||
|
|
||
Carbonyl Carbon Atom (carbonyl + carbon_atom)
Selected AbstractsTheoretical and Experimental Study of the Regioselectivity of Michael AdditionsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 2 2004David C. Chatfield Abstract Nucleophilic attack at an ,,,-unsaturated carbonyl moiety usually results in conjugate addition at the ,-carbon atom (1,4 or Michael addition) or, occasionally, in addition at the carbonyl carbon atom (1,2 addition). Recently, however, addition at the ,-carbon atom has been observed when strongly electron-withdrawing groups are positioned at the carbon atom , relative to the carbonyl group [e.g., methyl 3,3-bis(trifluoromethyl)propenoate (8) and ethyl 3-(2,4-dinitrophenyl)propenoate (24)]. We have performed theoretical calculations [HF/6,31+G(d) and B3LYP//HF/6,31+G(d)] for the addition of cyanide anion to model ,,,-unsaturated carbonyl compounds to determine trends in the regioselectivity with respect to properties of the substituents. The difference between the reaction barriers for ,- vs. ,-addition decreases as the strength of electron-withdrawing groups increases until, for sufficiently strong electron-withdrawing groups, ,-addition becomes favored. The calculations are in agreement with the experimental results. We show that the regioselectivity can be predicted from partial atomic charges and properties of the frontier orbitals of the reactants. We also report new experimental evidence of ,-addition to polysubstituted cinnamates and cinnamaldehydes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Synthesis of new fused isoquinolines via reissert compoundsJOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 6 2008Christian Fuchs Reissert compounds 2 derived from isoquinoline, chloroformates and TMS-cyanide were alkylated in position 1. The resulting alkylation products 3 as well as the precursors 2 reacted with Grignard reagents affording imidazoisoquinolines 4, 5, 7 and 8 by addition to the cyano group and Grignard reduction or by twofold addition to the cyano group, respectively. In both cases the alcohol of the 2-alkoxycarbonyl moiety was eliminated by attack of the N-atom at the carbonyl carbon atom. Under acid conditions, 1-benzylated Reissert compound 3h cyclised by attack of the resulting N-acyliminium C-atom at the o -position of the benzyl ring to form tetracyclic 1,3-bridged tetrahydroisoquinolines 10 and 11. Bromocyclisation of 1-allyl-2-menthyloxycarbonyl-substituted Reissert compounds 3b, c led to tricyclic dibromo products 12, in which the menthol moiety was split off and addition to the enamine double bond occurred. A 2-menthyloxycarbonyl group in Reissert compounds 2a and 3 failed to exert an asymmetric induction in all cases. [source] A study of the elimination of water from lithium-cationized tripeptide methyl esters by means of tandem mass spectrometry and isotope labelingRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 20 2006Erach R. Talaty Extensive isotope labeling (2H, 13C and 15N), collision-induced dissociation (CID) and multiple-stage tandem mass spectrometry were used to investigate the elimination of H2O from a series of model, metal-cationized tripeptide methyl esters. The present results corroborate our earlier suggestion that loss of water from lithiated peptides is initiated by a nucleophilic attack from the N-terminal side upon an amide carbonyl carbon atom to form a five-membered ring as an intermediate followed by 1,2-elimination of water. We show that the nucleophilic atom is the oxygen atom of the N-terminal amide group in the fragmentation of [AcGGGOMe+Li]+ as well as [GGGOMe+Li]+. However, the subsequent fragmentation is markedly different in the two cases as a result of the absence and presence of a free amino group. In particular, extensive scrambling of protons in the , -positions of GGGOMe is observed, presumably as a consequence of intervention of the basic amino group. Copyright © 2006 John Wiley & Sons, Ltd. [source] In Situ Synthesis of Trisubstituted Methanol Ligands and Their Potential as One-Pot Generators of Cubane-like Metal ComplexesCHEMISTRY - A EUROPEAN JOURNAL, Issue 27 2006Brendan F. Abrahams Dr. Abstract Two different one pot routes to a variety of metal cubane compounds are reported; one route is based on an in situ benzilic acid type rearrangement and the other involves in situ nucleophilic attack at a ketone. Diketosuccinic acid in basic solution in the presence of certain divalent metal ions undergoes a benzilic acid type rearrangement to generate the carbon oxyanion, C(CO2,)3O,, which serves as a cubane-forming bridging ligand in a series of octanuclear complexes of composition [M8{C(CO2)3O}4](H2O)12 (M=Mg, Mn, Fe, Co, Ni, Zn). At the heart of each of these highly symmetrical aggregates is an M4O4 cubane core, each oxygen component of which is provided by the alkoxo centre of a C(CO2,)3O, ligand. Reaction of 2,2,-pyridil, (2-C5H4N)COCO(2-C5H4N), and calcium nitrate in basic alcoholic solution, which proceeds by a similar benzilic acid type rearrangement, gives the cubane compounds, [Ca4L4(NO3)4] in which L=(2-C5H4N)2C(COOR)O, (R=Me or Et). Nucleophilic attack by bisulfite ion at the carbonyl carbon atom of 2,2,-dipyridyl ketone in the presence of certain divalent metals generates the electrically neutral complexes, [{(C5H4N)2SO3C(OH)}2M] (M=Mn, Fe, Co, Ni, Zn and Cd). Cubane-like complexes [M4{(C5H4N)2SO3C(O)}4] (M=Zn, Mn) can be obtained directly from 2,2,-dipyridyl ketone in one-pot reaction systems (sealed tube, 120,°C) if a base as weak as acetate ion is present to deprotonate the OH group of the initial [(C5H4N)2SO3C(OH)], bisulfite addition compound; the [(C5H4N)2SO3C(O)]2, ligand in this case plays the same cubane-forming role as the ligands C(COO,)3O, and (2-C5H4N)2C(COOR)O, above. When excess sodium sulfite is used in similar one-pot reaction mixtures, the monoanionic complexes, [M3Na{(C5H4N)2SO3C(O)}4], (M=Zn, Mn, Co) with an M3NaO4 cubane core, are formed directly from 2,2,-dipyridyl ketone. [source] | ||||||||||