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3
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77950497107
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University of Oxford, This account focuses on the reactions of sulfamate substrates; details of analogous reactions with carbamate substrates, that behave quite differently, will be published separately:
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S. L. Kostiuk, Chemistry Part II Thesis, University of Oxford, 2006
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(2006)
Chemistry Part II Thesis
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Kostiuk, S.L.1
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18
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69249135930
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F. J. Duran V. C. Edelsztein A. A. Ghini M. Rey H. Coirini P. Dauban R. H. Dodd G. Burton Bioorg. Med. Chem. 2009 17 6526
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Duran, F.J.1
Edelsztein, V.C.2
Ghini, A.A.3
Rey, M.4
Coirini, H.5
Dauban, P.6
Dodd, R.H.7
Burton, G.8
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42
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3042816129
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Blakey's group has studied analogous reactions of alkynyl sulfamates and has very recently extended those studies to encompass allenyl substrates to generate 1-alkyl-1-aminocyclopropanes:
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J. J. Shiers M. Shipman J. F. Hayes A. M. Z. Slawin J. Am. Chem. Soc. 2004 126 6868
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J. Am. Chem. Soc.
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Shiers, J.J.1
Shipman, M.2
Hayes, J.F.3
Slawin, A.M.Z.4
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46
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11144264532
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2 does not seem to be represented in the literature
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G. Prie N. Prevost H. Twin S. A. Fernandes J. F. Hayes M. Shipman Angew. Chem., Int. Ed. 2004 43 6517
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Prie, G.1
Prevost, N.2
Twin, H.3
Fernandes, S.A.4
Hayes, J.F.5
Shipman, M.6
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48
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0034835815
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Inclusion of one mole equivalent of propyl sulfamate in the reaction mixture with substrate 3 did not result in intermolecular amination, the allene being returned unchanged after work-up It is possible that the intermediate iminocyclopropane in this case survives the reaction conditions, by virtue of the presence of the iso-propyl group, and is hydrated during product isolation Assuming the reaction to follow the pathway suggested in Scheme 2, rotation of the terminal methyl-bearing carbon away from the N-bound dirhodium ligand, upon amination, would generate a U-shaped methyl,ethyl-substituted allyl cation that would be expected to close in a disrotatory fashion, giving rise to the observed (NOESY) stereochemistry
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C. G. Espino P. M. Wehn J. Chow J. Du Bois J. Am. Chem. Soc. 2001 123 6935
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Espino, C.G.1
Wehn, P.M.2
Chow, J.3
Du Bois, J.4
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49
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72649083171
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G. C. Feast J. Haestier L. W. Page J. Robertson A. L. Thompson D. J. Watkin Acta Crystallogr., Sect. C 2009 65 o635
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Feast, G.C.1
Haestier, J.2
Page, L.W.3
Robertson, J.4
Thompson, A.L.5
Watkin, D.J.6
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50
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9644254037
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3CN solution of each substrate was subjected to microwave heating first at 100 °C and then at 120 °C for 10-20 minutesat each temperature Quast first demonstrated the thermal interconversion of methylene aziridines and iminocyclopropanes, and showed that the latter cycloreverted rapidly to alkene and isocyanide at 190 °C:
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C. G. Espino K. W. Fiori M. Kim J. Du Bois J. Am. Chem. Soc. 2004 126 15378
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Espino, C.G.1
Fiori, K.W.2
Kim, M.3
Du Bois, J.4
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52
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0001895395
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The transformation 24 → 26 is analogous to the well-known reactions of chloroenamines with nucleophiles resulting in aminocyclopropane derivatives; for leading early work see:
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M. T. Reetz J. Rheinheimer J. Org. Chem. 1986 51 5465
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Reetz, M.T.1
Rheinheimer, J.2
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53
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2342608830
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Related reactions are described for example in ref. 19 and subsequent papers; however, apart from the examples in ref. 8c, we are aware of just a single paper describing the α-substitutions of 1-(N-sulfonylamino)-1- oxycyclopropane substrates:
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J. Szmuszkovicz E. Cerda M. F. Grostic J. F. Zieserl, Jr. Tetrahedron Lett. 1967 8 3969
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Szmuszkovicz, J.1
Cerda, E.2
Grostic, M.F.3
Zieserl Jr., J.F.4
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