Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Patent
1993-07-30
1996-03-12
Shaver, Paul F.
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
556406, 556449, 556465, 556 95, 260665R, 585360, 585407, 585361, 585350, 568367, 568374, 568376, 568379, 568381, 568816, 568819, 568822, 568832, 568838, 568839, 568853, 568857, 5689095, 564305, 564374, 548408, 548512, 548553, 562433, 562435, 549265, 549273, 549295, 549283, 549302, 549328, 570186, C07F 708, C07F 722, C07F 724, C07F 730
Patent
active
054987342
ABSTRACT:
The magnesium complexes of cyclic hydrocarbons containing conjugated dienes, such as 1,2-dimethylenecycloalkanes, and 1,3-butadienes, are readily prepared in high yields using highly reactive magnesium. Reactions of these (2-butene-1,4 diyl)magnesium reagents with electrophiles such as dibromoalkanes, alkylditosylates, alkylditriflates, bromoalkylnitriles, esters, or amides serve as a convenient method for synthesizing carbocyclic systems. Significantly, carbocycles prepared by this method contain functional groups such as the exocyclic double bond or a keto group in one of the rings which could be used for further elaboration of these molecules. Furthermore, fused bicyclic systems containing a substituted five-membered ring can be conveniently prepared at high temperatures by the reactions of (2-butene-1,4-diyl)magnesium complexes with carboxylic esters or acid halides whereas low temperatures lead to regioselective synthesis of .beta.,.gamma.-unsaturated ketones. Additionally, .gamma.-lactones, including spiro .gamma.-lactones, can be easily prepared in a one pot synthesis from the reaction of (2-butene-1,4-diyl)magnesium complexes with a ketone or aldehyde and carbon dioxide. Also, .delta.-lactones can be easily prepared in a one pot synthesis from the reaction of (2-butene-1,4-diyl)magnesium complexes with epoxides followed by reaction with CO.sub.2. Use of .alpha.-hydroxy epoxides without the addition of CO.sub.2 leads to the synthesis of vicinal diols. Chiral epoxides lead to chiral alcohols.
REFERENCES:
patent: 3388179 (1968-06-01), Ramsden
patent: 4069267 (1978-01-01), Kamienski et al.
patent: 4087468 (1978-05-01), Solomon
patent: 4166898 (1979-09-01), Kambe et al.
patent: 4325840 (1982-04-01), Malpass
patent: 4396554 (1983-08-01), Robinson et al.
patent: 4731203 (1988-03-01), Bogdanovic
patent: 5211886 (1993-05-01), Rieke
patent: 5211889 (1993-05-01), Rieke
patent: 5231205 (1993-07-01), Rieke
M. T. Arencibia et al., "Hypervalent Organoiodine Compounds: Radical Fragmentation of Oxabicyclic Hemiacetals. Convenient Synthesis of Medium-sized and Spiro Lactones", J. Chem. Soc. Perkin Trans., 1, 3349-3360 (1991).
S. Akutagawa et al., "Metal-Assisted Terpenoid Synthesis. 3. A Myrcene Magnesium Compound as a New Example of an Enediylmetal System Formed from a Conjugated Diene and Its Synthetic Applications," J. Am. Chem. Soc., 98, 7420-7421 (1976).
R. Baker et al., "Reaction of 'Myrcene-Magnesium' with Esters, Acetyl Chloride, and Acetic Anhydride: Formation of Cyclopentenols and Cyclopropane Derivatives," J. C. S. Perkin I, 1815-1818 (1976).
N. C. Barua et al., "A Convenient Synthesis of .delta.-Lactones", Synthesis, 1067-1070 (1986).
B. Bogdanovic, "Magnesium Anthracene Systems and Their Application in Synthesis and Catalysis," Acc. Chem. Res., 21, 261-267 (1988).
T. P. Burns et al., "Preparation of Grignard Reagents from 3-Halo Ethers," J. Org. Chem., 48, 4141-4143 (1983).
T. P. Burns et al., "Highly Reactive Magnesium and Its Application to Organic Syntheses," J Org. Chem., 52, 3674-3680 (1987).
P. Cononne et al., "Reaction of Dibromoagnesio)Alkanes with Unsymmetrically Substituted Cyclic Anhydrides", Tetrahedron Lett., 21, 4167-4170 (1980).
P. Cononne et al., "One-Step Spiroannelation, Synthesis of Spiro .gamma.- and .delta.-Lactones", J. Org. Chem., 46, 3091-3097 (1981).
J. E. Dubois et al., "Magnesiens encombres a structure cage: synthese du bromure d'adamantyl-1 magnesium," C. R. Acad. Sci. Ser., 284, 145-148 (1977).
U. M. Dzemilev et al., "Synthesis and Transformations of 'Non-Grignard' Organomagnesium Reagents Obtained from 1,3-Dienes," J. Organomet. Chem., 406, 1-47 (1991).
E. Erdik, "Copper(I) Catalyzed Reactions of Organolithiums and Grignard Reagents," Tetrahedron, 40, 641-657 (1984).
G. Erker et al., "The Remarkable Features of (.eta..sup.4 -Conjugated Diene)zirconocene and -hafnocene Complexes," Adv. Organomet. Chem., 24, 1-39 (1985).
C. J. Francis et al., "Preparations of Chiral .delta.-Lactones via Enantiotopically Specific Pig Liver Esterase-catalyzed Hydrolyses of 3-Substituted Glutaric Acid Diesters", J. Chem. Soc., Chem. Commun., 579-580 (1984).
P. K. Freeman et al., "Magnesium Anthracene Dianion," J. Org. Chem., 48, 879-881 (1983).
K. Fujita et al., "Magnesium-Butadiene Addition Compounds: Isolation, Structural Analysis and Chemical Reactivity," J. Organomet. Chem., 113, 201-213 (1976).
B. H. Han, "Organic Sonochemistry. Ultrasound Acceleration of the Preparation of Highly Active Mg and Zn Powders," J. Korean Chem. Soc., 29, 557-558 (1985).
S. Harvey et al., "Main Group Conjugated Organic Anion Chemistry. 3. Application of Magnesium-Anthracene Compounds in the Synthesis of Grignard Reagents," J. Org. Chem., 53, 3134-3140 (1988).
S. Harvey, et al., "Polymer Supported 'Magnesium(anthracene)': Effective in Forming Benzylic Grignard Reagents (via Electron Transfer Reactions)," J. C. S., Chem. Commun., 652-653 (1988).
Y. Kai et al., "The X-Ray Structure of a Magnesium-1,3-Diene Complex, The Unique Mode of Coordination of Diene Observed in Penta-Coordinated Mg(THF).sub.3 (s-cis-PhCH.dbd.CH-CH.dbd.CHPh)," Chem. Lett., 1277-1280 (1982).
S. Kano et al., "A Synthesis of .gamma.-Butyrolactone and Related Compounds", Heterocycles, 14, 661-711 (1980).
D. W. Knight, "Saturated Carbocyclic Ring Synthesis," Gen. Synth. Methods, 6, 277-311 (1983).
K. Kobayashi et al., "A New Route to .gamma.-Substituted .gamma.-Lactones and .delta.-Substituted .delta.-Lactones Based on the Regioselective .beta.-Scission of Alkoxyl Radicals Generated from Transannular Hemiacetals", Tetrahedron, 47, 7245-7258 (1991).
N. A. Le et al., "Reaction of Photochemically Generated Dibromocarbene with 1,2-Dimethylenecycloalkanes. 1,4 Addition is Real", J. Am. Chem. Soc., 111, 8491-8493 (1989).
W. E. Lindsell, "Magnesium, Calcium, Strontium and Barium," Comprehensive Organometallic Chemistry, Ch. 4.1 and 4.2; Wilkinson, Stone & Abel, ed.; Pergamon Press, Oxford (1982); pp. 155-252.
B. H. Lipshutz et al., "Reactions of Stoichiometric Higher Order, Mixed Lithio Magnesio Organocuprates," Tetrahedron, 42, 2873-2879 (1986).
R. M. Magid, "Nucleophilic and Organometallic Displacement Reactions of Allylic Compounds: Stereo- and Regiochemistry," Tetrahedron, 36, 1901-1930 (1980).
G. D. Maio et al., ".delta.-Lactones from .delta.-Ketoesters--II", Tetrahedron, 40, 749-755 (1984).
P. Markov et al., "Uber die Reduktion des Naphthalins mit Magnesium in Flussigem Ammoniak," Liebigs Ann. Chem., 704, 126-132 (1967).
P. Markov et al., "Reactions of Calcium and Magnesium Naphthalenides with Ethyl Esters of 2-Bromopropionic and 2-Bromobutyric Acid in Liquid Ammonia," J. Organomet. Chem., 81, 1-6 (1974).
P. Markov et al., "Uber die Reaktion von Biphenyl mit Magnesium in flussigem Ammoniak," Monatshefte fur Chemie, 107, 619-624 (1976) (with English language abstract).
K. Mori et al., "Synthesis of Optically Active Pheromones", Tetrahedron, 45, 3233-3298 (1989).
S.-I. Murahashi et al., "Ruthenium-Catalyzed Oxidative Transformation of Alcohols and Aldehydes to Esters and Lactones", J. Org. Chem., 52, 4319-4327 (1987).
Y. Nakano et al., "On the Reaction Between Magnesium and Iosprene," Tetrahedron Lett., 28, 2833-2836 (1972).
E. Negishi, "Bimetallic Catalytic Systems Containing Ti, Zr, Ni, and Pd. Their Applications to Selective Organic Synthesis," Pure & Appl. Chem., 53, 2333-2356 (1981).
D. J. Ramon et al., "Direct Synthesis of .delta.-Lactones from 2-(3-lithiopropyl)-1,3-Dioxolane and Carbonyl Compounds", Tetrahedron Lett., 31, 3767-3770 (1990).
C. L. Raston et al., "Magnesium Anthracene: An Alternative to magnesium in the High Yield Synthesis of Grignard Reagents," J. Chem. Soc., Chem. Commun., 1702-1703 (1984).
R. Rathore et al., "Substituent Directed Oxidative Cyclization with Cetyltrimethylammonium Permanganate: A General Approach to the Synthesis of .gamma.- and .delta.-Lactones", Tetrahedron Lett., 27, 4079-4082 (1986).
W. J. Richter, "Diorganosilacyclopent-3-ene Derivatives from Diorganodichlorosilanes and Butadienemagnesium: Evidence for Crotyl-Grignard Intermediates," J. Organomet. Chem., 289, 45-49 (1985).
R.
Shaver Paul F.
University of Nebraska
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