-
10
-
-
84914011550
-
-
Herein referred to as simply “oxazoline.” The 3- and 4-oxazolines have distinctive characteristics wholly unrelated to the 2-oxazolines as described in this article. A comparison of the related heterocycles.
-
-
-
-
18
-
-
0001015289
-
Tertiäres Phosphan/Tetrachlormethan, ein vielseitiges Reagens zur Chlorierung, Dehydratisierung und PN-Verknüpfung
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Angewandte Chemie
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Appel1
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85
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0000224388
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A number of elegant mechanistic as well as target-oriented studies have been carried out. See:
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Pastor1
Togni2
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85082976445
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Palladium-Catalyzed Coupling of Oxazol-2-yl- and 2-Oxazolin-2-yltrimethylstannanes with Aromatic Halides. A New Entry to 2-Aryl and 2-Heteroaryl Oxazoles and Oxazolines
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(1987)
Synthesis
, pp. 693
-
-
Dondoni1
Fantin2
Fogagnolo3
Medici4
Pedrini5
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137
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84914011546
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A. I. Meyers and F. Tevaras - studies are in progress to utilize photochemical oxidative routes to accomplish this transformation.
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146
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0025874122
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A practical and efficient method for the construction of the biphenyl framework; nucleophilic aromatic substitution on 2-methoxybenzoates with aryl grignard reagents
-
For example: Hindered esters have been used for this purpose, though subsequent hydrolysis is difficult except in intramolecular lactonizations, thus limiting the generality of this approach
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Journal of the Chemical Society, Chemical Communications
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Hattori1
Suzuki2
Miyano3
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147
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85018408737
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Oxazoles are masked carboxyls that activate ortho-leaving groups in nucleophilic aromatic substitution.
-
Oxazoles have also been used with a measure of success:
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(1987)
Chemistry Letters
, pp. 19
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Cram1
Bryant2
Doxsee3
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148
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33845470262
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The methoxide displacement is observed more frequently in the literature most certainly due to the greater availability of the appropriate starting materials. The fluoride group often allows coupling at more sterically-conjested sites. For example, see:
-
(1984)
J. Am. Chem. Soc.
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, pp. 4987
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Cram1
Katz2
Dicker3
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84914011545
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PCT Int. Appl. WO 84 02,903 (Cl. C07C59/56), 02 Aug 1984, US Appl. 460,600, 24 Jan 1983
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Chem. Abstr.
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-
Anderson1
Sandoz2
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183
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0001393776
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It has been observed that organolithium reagents behave quite differently when freshly generated for immediate use. Many mixtures that failed to react were found to react quite well if the lithium reagent was formed in situ. This behavior suggests changes in aggregation of the reagent over time affording a complex with typically lower reactivity. This problem has been circumvented through the use of vinyltin reagents as precursors to vinyllithiums:, An increase in reactivity of other organolithium reagents was also observed when generated from “Freeman's reagent” (LiDBB):
-
(1988)
Tetrahedron
, vol.44
, pp. 3107
-
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Meyers1
Lutomski2
Laucher3
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200
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85095724444
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Tricarbonylchromium Phenyloxazoline and -Imine Complexes: Highly Regioselectiveortho-Additions of Carbon Nucleophiles
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(1991)
Synlett
, pp. 657
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Kundig1
Amurrio2
Liu3
Ripa4
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202
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37949026940
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Diastereoselektive Synthese substituierter Cyclohexadiene aus enantiomerenreinen Tricarbonyl(2-phenyl-4,5-dihydrooxazol)chrom-Komplexen
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Angewandte Chemie
, vol.104
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Kundig1
Ripa2
Bernardinelli3
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206
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0002139663
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Regioselective Additions to 3-(Oxazolinyl)pyridine with Organolithium Reagents
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(1982)
HETEROCYCLES
, vol.18
, pp. 13
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-
Meyers1
Natale2
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208
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0002435590
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Chiral Aminal Templates 5.1Preparation of Chiral 1,4-Dihydropyridine-3-carboxaldehydes
-
In a related approach, an achiral oxazoline was used in addition to a chiral nitrogen-alkylating moiety. Low enantiomeric enrichment was obtained:
-
(1991)
Synlett
, pp. 111
-
-
Gosmini1
Mangeney2
Alexakis3
Commercon4
Normant5
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211
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0000227799
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The first example of a non-enzymic stereospecific intramolecular reduction by an NADH mimic containing a covalently bound carbonyl moiety was accomplished through this method:
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(1987)
J. Am. Chem. Soc.
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, pp. 3155
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Meyers1
Brown2
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213
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0012397313
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An excellent review covering primarily the tertiary amide and carbamate metalation directors has appeared with introductory remarks referencing similar directing groups:
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(1990)
Chem. Rev.
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, pp. 879
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Snieckus1
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2042487195
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For a more detailed discussion of the concept of complex-induced proximity effects, see:
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Acc. Chem. Res.
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-
-
Beak1
Meyers2
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232
-
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0027324433
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-
For a prior example of an intermolecular asymmetric Ullmann reaction (2–13% de), see:
-
(1993)
Tetrahedron Lett.
, vol.34
, pp. 3061
-
-
Nelson1
Meyers2
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233
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0001985533
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Partial asymmetric synthesis of atropisomeric 1,1'-binaphthyls via the Ullmann coupling reaction of chiral alcohol esters of 1-bromo-2-naphthoic acid.
-
For prior examples of intramolecular asymmetric Ullmann reactions (⪢99% ee), see:
-
(1980)
Chemistry Letters
, pp. 1027
-
-
Miyano1
Tobita2
Suzuki3
Nishikawa4
Hashimoto5
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247
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84986495511
-
Alkyl nitrate nitration of active methylene compounds. Nitration of 2-substituted 2-oxazolines
-
The standard 2-alkyloxazoline metalation is still used extensively, for example:
-
(1986)
Journal of Heterocyclic Chemistry
, vol.23
, pp. 825
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-
Feuer1
Bevinkatti2
Luo3
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274
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0002755327
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Regioselective Synthesis of 2-Hydroperoxy-2-methylenebutanoic Acid Derivatives via Photooxygenation of Tiglic Acid Derivatives
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(1986)
Synthesis
, pp. 1050
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Adam1
Griesbeck2
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312
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9144262142
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Dioxolanylium Ions Derived from Carbohydrates. X. Nucleophilic trans Opening with the Trichloroacetimidoyl Neighbouring Group.
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Acta Chemica Scandinavica
, vol.40 B
, pp. 493
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Jacobsen1
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313
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9144258948
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Dioxolanylium Ions Derived from Carbohydrates. XI. Aminosugar Formation by trans Opening with the Trichloroacetimidoyl Neighbouring Group.
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Acta Chemica Scandinavica
, vol.40 B
, pp. 498
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Jacobsen1
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314
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0342541987
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Rearrangement of Carbohydrate Epoxides to Amino Sugars Using a Trichloroacetimidoyl Neighboring Group.
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Acta Chemica Scandinavica
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, pp. 605
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Jacobsen1
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327
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12944335379
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2-Ethyl-4,5-dihydro-1,3-oxazole: A Useful Aziridine Equivalent for the Preparation of Substituted 1,2-Ethanediamines
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(1981)
Synthesis
, pp. 541
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Poindexter1
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344
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0000829319
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These oxazolines were subsequently employed as ligands in cuprate additions to cyclohexenone with similarly low enantiomeric excesses (10–20%):, Ordinary, achiral, 2,4,4-trimethyl-2-oxazoline has been used as ligand in cuprate additions as well:
-
(1986)
J. Org. Chem.
, vol.51
, pp. 4953
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-
Bertz1
Dabbagh2
Sundararajan3
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347
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0000980726
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Bis(4,5-dihydrooxazolyl)-Derivate in der asymmetrischen Katalyse
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Angewandte Chemie
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Bolm1
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84989533217
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C 2-Symmetric Bioxazolines and Bithiazolines as New Chiral Ligands for Metal Ion Catalyzed Asymmetric Syntheses: Asymmetric Hydrosilylation
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(1991)
Synlett
, pp. 257
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-
Helmchen1
Krotz2
Ganz3
Hansen4
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365
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84987472013
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C2-Symmetric 4,4?,5,5?-Tetrahydrobi(oxazoles) and 4,4?,5,5?-Tetrahydro-2,2?-methylenebis[oxazoles] as Chiral Ligands for Enantioselective Catalysis Preliminary Communication
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, pp. 232
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Muller1
Umbricht2
Weber3
Pfaltz4
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368
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0000146695
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Chirale Phosphinoaryldihydrooxazole als Liganden in der asymmetrischen Katalyse: Pd-katalysierte allylische Substitution
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(1993)
Angewandte Chemie
, vol.105
, pp. 614
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von Matt1
Pfaltz2
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370
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0001064399
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Palladium-katalysierte, enantioselektive allylische Substitutionen
-
For a mechanistic analysis, see
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(1993)
Angewandte Chemie
, vol.105
, pp. 576
-
-
Reiser1
-
416
-
-
0026680496
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-
A review of oxazole-containing natural products has appeared, covering many species possessing oxazoline moieties as well:, Similarly, a review of marine metabolites has indirectly addressed this topic:
-
(1992)
Heterocyclic Chem.
, vol.29
, pp. 607
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-
Pattenden1
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