Intermolecular insertion of an N,N-heterocycIic carbene into a nonacidic C-H bond: Kinetics, mechanism and catalysis by (K-HMDS)2 (HMDS = Hexamethyldisilazide)

Chemistry - A European Journal

Volumn 12, Issue 20, 2006, Pages 5361-5375

  Lloyd Jones, Guy C ^a   Alder, Roger W ^a   Owen Smith, Gareth J J ^a  

^a UNIVERSITY OF BRISTOL   (United Kingdom)

Author keywords

Carbenes; Homogeneous catalysis; Isotope effects; Kinetics; Potassium

Indexed keywords

CATALYSIS; MOLECULAR DYNAMICS; MOLECULAR STRUCTURE; POTASSIUM COMPOUNDS; REGRESSION ANALYSIS; TOLUENE;

CARBENES; HOMOGENEOUS CATALYSIS; ISOTOPE EFFECTS; SOLVENT CAGE;

OLEFINS;

EID: 33745899030     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200600266     Document Type: Article

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148. a(b-x))-1)]/ (2a))/
149. a=
150. 0+
151. 0=0], the simplified binding isotherm and the associated simplified NMR-shift relationship, see: See E.V. Ansyln, D. A. Dougherty in Modern Physical Organic Chemistry, University Science Books, Sausilito, California, USA, 2006, pp. 216-221.
152. 2], in which 2′ is the NN′-diisopropyl analogue of 2, has been isolated and its structure determined by X-ray diffraction-see reference [25a]. This structure may of course arise through the favourable symmetry/packing/packing forces in the bis-carbene KHMDS dimer complex allowing crystallisation of the minor component of the three-stage equilibrium.
153. [Dg]tol=9.5±0.8 is suggestive of a solvent KIE of about 1.2. Whilst such effects are common with protic solvents that can effect deuteration at exchangeable reaction sites, and are thus accountable by for example, proton inventory (see for example, R. L. Schowen, Prog. Phys. Org. Chem. 1972, 9, 275-332)
154. substantial solvent KIEs in aprotic media are rather rare - see for example b) L. R. Khundkar, J. W. Perry, J. E. Hanson, P. B. Dervan, J. Am. Chem. Soc. 1994, 116, 9700-9709;
155. c) Y. Zong, J.L. McHale, J. Chem. Phys. 1997, 106, 4963-4973;
156. 0]toluene ratio.
157. See for example, A. Streitweiser, Jr., P. H. Owens, G. Sonnichsen, W. K. Smith, G. R. Ziegler, H. M. Niemeyer, T. L. Kruger, J. Am. Chem. Soc. 1973, 95, 4254-4257.
158. 2] amounts to 60-80 mM and thus about 75% of 2 is complexed. We have not determined KIEs for the individual reactions of free 2 and complexed 2.
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164. The NN′-diethyl and NN′-diisopropyl analogues of 2 undergo analogous reaction with toluene; G. C. Lloyd-Jones, G. J. J. Owen-Smith, unpublished results.
165. 2O at 140°C. The resulting tetrahydropyrimidine intermediate was reduced with DIBAL-H in toluene to afford N-ethyl-N′-isopropyl-1,3-diaminopropane.
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