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Volumn 30, Issue 5, 1991, Pages 477-515

The Isoinversion Principle—a General Model of Chemical Selectivity

Author keywords

Isoinversion principle; Reaction mechanisms; Selectivity; Stereoselectivity

Indexed keywords

ORGANIC COMPOUND;

EID: 0025780257     PISSN: 05700833     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.199104771     Document Type: Review
Times cited : (350)

References (595)
  • 1
    • 84990074495 scopus 로고    scopus 로고
    • Lectures before the Société Chimique de Paris on January 20 and February 3, 1860
    • Pasteur, L.1
  • 28
    • 0039342885 scopus 로고
    • Funktionelle Gruppen in konkaver Lage: Asymmetrische Diels-Alder-Synthese mit nahezu vollständiger (Lewis-Säure-katalysiert) und hoher (unkatalysiert) Stereoselektivität
    • (1981) Angewandte Chemie , vol.93 , pp. 208
    • Helmchen, G.1    Schierer, R.2
  • 33
    • 0000442517 scopus 로고
    • Methoden der asymmetrischen Synthese – enantioselektive katalytische Hydrierung
    • (1971) Angewandte Chemie , vol.83 , pp. 956
    • Izumi, Y.1
  • 64
  • 73
    • 84990154806 scopus 로고    scopus 로고
    • (b) Merck‐Schuchardt, MS‐INFO 85‐17 (8‐phenylmenthol).
  • 92
    • 0000261040 scopus 로고
    • Enantioselective Syntheses of ?-Amino Acids from 10-(Aminosulfonyl)-2-bornyl Esters and Di(tert-butyl) Azodicarboxylate. Preliminary Communication
    • (1986) Helvetica Chimica Acta , vol.69 , pp. 1923
    • Oppolzer, W.1    Moretti, R.2
  • 114
    • 84990157183 scopus 로고    scopus 로고
    • See Ref. [7], p. 275.
  • 117
    • 84990153982 scopus 로고    scopus 로고
    • Dissertation, Technische Hochschule Aachen 1984.
    • Koch, H.1
  • 142
    • 0000007957 scopus 로고
    • The Photocycloaddition of Carbonyl Compounds to Unsaturated Systems: The Syntheses of Oxetanes
    • (1968) Adv. Photochem. , vol.6 , pp. 301
    • Arnold, D.R.1
  • 166
    • 84990081381 scopus 로고
    • Dissertation, Technische Hochschule Aachen
    • (1987)
    • Weuthen, M.1
  • 167
    • 84990123030 scopus 로고
    • Dissertation, Technische Hochschule Aachen
    • (1988)
    • Vassen, R.1
  • 168
    • 84990132373 scopus 로고
    • Dissertation, Technische Hochschule Aacben
    • (1991)
    • Buschmann, H.1
  • 169
    • 84990132375 scopus 로고    scopus 로고
    • Diplomarbeit, Technische Hochschule Aachen 1986.
    • Hoffmann, N.1
  • 170
    • 84990132380 scopus 로고    scopus 로고
    • 13C‐NMR spectrum according to (24), where c is the concentration of the major diastereomer, and c′ the concentration of the minor diastereomer in the product mixture. Depending on the system, between 14 and 16 pairs of signals can be drawn on for determination of the de value. The de values given in Table 1 are averages of several independent measurements. By using this technique, the influence of nuclear Overhauser and spin relaxation effects can be kept to a minimum.
  • 179
    • 84990162398 scopus 로고
    • Dissertation, Technische Hochschule Aachen
    • (1991)
    • Plath, M.W.1
  • 180
    • 0001728892 scopus 로고
    • Methoden der Reaktivitätsumpolung
    • (a) The concepts of diastereo‐ and regioselectivity are used in the sense of D. Seebach's definition.
    • (1979) Angewandte Chemie , vol.91 , pp. 259
    • Seebach, D.1
  • 186
    • 84990136179 scopus 로고    scopus 로고
    • It should be noted here that in this correlation the rate constant quotients obtained from the diastereomeric excesses have been related to those of the unsubstituted system. This affects the ϱ value found, in that the σ values (defined as quotients of the equilibrium constants for the substituted or unsubstituted systems) are taken from references where they had been determined by direct quotient formation from the rate constants for substituted or unsubstituted systems.
  • 207
    • 0011764239 scopus 로고
    • Die Bedeutung isoselektiver Temperaturen für die Existenz linearer Freie-Energie-Beziehungen
    • (1980) Angewandte Chemie , vol.92 , pp. 864
    • Giese, B.1
  • 211
    • 84980149876 scopus 로고
    • Zur Temperaturabhängigkeit der Selektivität von π-und σ-Radikalen
    • 161, 723
    • (1976) Angewandte Chemie , vol.88 , pp. 159
    • Giese, B.1
  • 212
  • 223
    • 84990161403 scopus 로고    scopus 로고
    • The presence of an inversion point in temperature‐dependent regioselectivity was not recognized by us in the original publication. [34] A new analysis of the original experimental data in the light of the isoinversion relationship, however, indicated the existence of an inversion point in the Eyring diagram.
  • 224
    • 84990161404 scopus 로고    scopus 로고
    • At this point, the usefulness in mechanistic studies of auxiliaries that yield diastereomeric excesses in the low to middle range should be noted. Middle range de values are especially sensitive to small variations in reactant structure and/or minor changes in reaction conditions [36, 37].
  • 231
    • 84990162855 scopus 로고    scopus 로고
    • See Ref. [6], p. 40.
  • 233
    • 84982058543 scopus 로고
    • Asymmetrische Synthesen mit Ketenen, VII1)Tertiäre Amine mit einem asymmetrischen C-Atom als Katalysatoren für die asymmetrische Synthese von α-Phenyl-propionsäure-methylester
    • (1969) Justus Liebigs Annalen der Chemie , vol.722 , pp. 1
    • Pracejus, H.1    Kohl, G.2
  • 240
    • 84956733937 scopus 로고
    • Kinetik und Mechanismus katalytischer Additionsreaktionen an kumulierte Doppelbindungssysteme, III. Tieftemperaturkinetik, H-Isotopeneffekte und Verlauf aminkatalysierter Additionen von Alkoholen an Phenylmethyl- und Diphenylketen
    • (1967) Chemische Berichte , vol.100 , pp. 196
    • Tille, A.1    Pracejus, H.2
  • 255
  • 260
    • 84990158706 scopus 로고    scopus 로고
    • See Ref. [91].
  • 272
    • 0001213707 scopus 로고
    • Asymmetrische Synthesen mit Ketenen, III. Über den Lösungsmitteleinfluß auf den sterischen Ablauf zweier asymmetrischer Amidsynthesen
    • (1963) Chemische Berichte , vol.96 , pp. 854
    • Pracejus, H.1    Tille, A.2
  • 274
    • 84990155792 scopus 로고    scopus 로고
    • See Ref. [6], p. 276f.
  • 276
    • 84990152966 scopus 로고    scopus 로고
    • See Ref. [7], p. 53.
  • 277
    • 84990111261 scopus 로고    scopus 로고
    • See Ref. [6]. p. 160 ff. and 297 ff.
  • 361
    • 0039314238 scopus 로고
    • Cob(I)alamin as Catalyst. 8th Communication. Cob(I)alamin and Heptamethyl Cob(I)yrinate During the Reduction of ?,?-Unsaturated Carbonyl Derivatives
    • (1980) Helvetica Chimica Acta , vol.63 , pp. 1628
    • Fischli, A.1    Daly, J.J.2
  • 363
    • 2342499124 scopus 로고
    • Asymmetric hydrogenation catalyzed by the (achiral base)bis(dimethylglyoximato)cobalt(II)-chiral cocatalyst system. The preparation of a new type of chiral cocatalyst and its application to the asymmetric hydrogenation of methyl N-(acetylamino)acrylate and benzil.
    • (1981) Bulletin of the Chemical Society of Japan , vol.54 , pp. 2136
    • Takeuchi, S.1    Ohgo, Y2
  • 368
    • 0000796288 scopus 로고
    • Asymmetrische Hydrierung von α-(Acetylamino)zimtsäure mit einem neuen Rhodiumkomplex; die Konzeption eines optimalen Liganden
    • (1984) Angewandte Chemie , vol.96 , pp. 425
    • Nagel, U.1
  • 370
    • 0000652292 scopus 로고
    • Enantioselektive Katalyse, 4. SyntheseN-substituierter (R,R)-3,4-Bis(diphenylphosphino)-pyrrolidine und Anwendung ihrer Rhodiumkomplexe zur asymmetrischen Hydrierung von α-(Acylamino)acrylsäure-Derivaten
    • (1986) Chemische Berichte , vol.119 , pp. 3326
    • Nagel, U.1    Kinzel, E.2    Andrade, J.3    Prescher, G.4
  • 371
    • 0000119119 scopus 로고
    • Enantioselektive Katalyse, 5. Neue Liganden mit vier Stereozentren. Synthese und Trennung der drei diastereomeren [P(R,S),3R,4R,P′(R,S)]-3,4-Bis(methylphenylphosphino)-pyrrolidine
    • (1988) Chemische Berichte , vol.121 , pp. 1123
    • Nagel, U.1    Rieger, B.2
  • 372
    • 4243385107 scopus 로고
    • The δ/λ conformation of the RhPCCP five‐membered ring is defined as in the corresponding structural element MNCCN in numerous ethylene‐diamine complexes; cf. The Commission on the Nomenclature of Inorganic Chemistry of the International Union of Pure and Applied Chemistry
    • (1970) Inorg. Chem. , vol.9 , pp. 1
  • 373
    • 84990120804 scopus 로고    scopus 로고
    • According to Brown et al., in seven‐membered chelate rings the product configuration is determined by the chair or twist‐boat conformation of the catalyst complex. Starting from (Z)‐enamides, the chair conformation yields (S)‐amino acids, whereas the twist‐boat form leads to the(R)‐enantiomer [173 a]
  • 413
    • 84990117477 scopus 로고    scopus 로고
    • See Ref. [7], p. 100.
  • 414
    • 84990117484 scopus 로고    scopus 로고
    • See Ref. 161, p. 302.
  • 422
    • 84990152512 scopus 로고    scopus 로고
    • 5).
  • 444
    • 0345956770 scopus 로고
    • The role of molecular shape similarity in specific molecular recognition
    • (1985) Top, Curr. Chem. , vol.128 , pp. 91
    • Endo, T.1
  • 451
    • 84984360285 scopus 로고
    • Enantioselektive Addition von Organometallreagentien an Carbonylverbindungen: Übertragung, Vervielfältigung und Verstärkung der Chiralität
    • (1991) Angewandte Chemie , vol.103 , pp. 34
    • Noyori, R.1    Kitamura, M.2
  • 468
    • 84990078369 scopus 로고    scopus 로고
    • (c) Ref. [256]
  • 470
    • 84990095175 scopus 로고    scopus 로고
    • See Ref. [256d, e].
  • 479
    • 84990095185 scopus 로고    scopus 로고
    • (a) See Ref. [87]
  • 486
    • 84990139231 scopus 로고    scopus 로고
    • (a) [158]
  • 488
    • 26444466057 scopus 로고
    • According to H. Wynberg, the use of racemic auxiliaries for determining de values is only permissible to a first approximation. Because of the presence of chiral reagents, the medium itself becomes chiral, giving a chiral solvent effect. In a racemic system, the interactions of the enantiomers with each other (RR, RS and SS interactions) can lead to differing asymmetric induction
    • (1976) Tetrahedron , vol.32 , pp. 2831
    • Wynberg, H.1    Feringa, B.2
  • 489
    • 84990095202 scopus 로고    scopus 로고
    • The analysis of the data for pressure‐dependent selectivity measurements must be treated with caution in some cases, since the experimental details for the measurements were not given in the literature. The appearance of the inversion points described could hence also be due to non‐uniform experimental conditions. We thank R. Selke for this observation.
  • 508
    • 0342706214 scopus 로고
    • The enantioface-differentiating (asymmetric) hydrogenation of the C=O double bond with modified raney nickel. XXXIV. The adsorption mode of 2-hydroxy acid on Raney nickel.
    • (1980) Bulletin of the Chemical Society of Japan , vol.53 , pp. 1019
    • Harada, T.1
  • 509
    • 84990148920 scopus 로고
    • Dissertation, Technische Universität München
    • (1986)
    • Youn, J.‐H.1
  • 510
    • 25344475195 scopus 로고
    • Basekatalysierte asymmetrische Induktion der Reaktion von Methyl(phenyl)keten mit 1-Phenylethanol: Gewinnung von Hydratropasäure in hoher Enantiomerenreinheit
    • (1981) Angewandte Chemie , vol.93 , pp. 919
    • Jähme, J.1    Rüchardt, C.2
  • 533
    • 0001381075 scopus 로고
    • Asymmetric Reductions with Chiral Complex Aluminum Hydrides and Tricoordinate Aluminum Reagents
    • (1983) Top. Stereochem. , vol.14 , pp. 231
    • Haubenstock, H.1


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