Soluble highly reactive form of calcium and reagents thereof

Chemistry of carbon compounds – Miscellaneous organic carbon compounds – C-metal

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549263, 549264, 549265, 549273, 549275, 546 16, 585502, 585520, C07F 304, C07D30500, C07D30900, C07C 202

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active

053840780

ABSTRACT:
A soluble highly reactive form of calcium, prepared from Ca(II) salts and a reducing agent in ethereal, polyethereal, or hydrocarbon solvents, is presented. This form of calcium can be used in the preparation of organocalcium reagents. The organocalcium reagents resulting from the reaction of the soluble highly reactive calcium with organic compounds containing either halide, cyanide, a 1,3-diene, or a polyunsaturated functionality, are stable, useful reagents for organic synthesis. The organocalcium halide reagents undergo Grignard-type reactions. They also undergo reactions with Cu(I) salts to form organocalcium cuprate reagents. The organocalcium cuprate reagents undergo a variety of cross-coupling reactions. The soluble highly reactive calcium reacts with 1,3-dienes to yield the corresponding 2-butene-1,4-diylcalcium complexes. These bis-organocalcium reagents can undergo dialkylation reactions with .alpha.,.omega.-alkylene dihalides and dichlorosilanes to form the corresponding 3-, 5-, and 6-membered ring derivatives. The soluble highly reactive calcium also reacts with organic dihalides to form mono- or diorganocalcium compounds which can be converted into a wide variety of polymers.

REFERENCES:
patent: 4069267 (1978-01-01), Kamienski et al.
patent: 4087468 (1978-05-01), Solomon
patent: 4166898 (1979-09-01), Kambe
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: 5231205 (1993-07-01), Rieke
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).
A. Alexakis et al., "Organocopper Conjugate Addition Reaction in the Presence of Trimethylchlorosilane," Tetrahedron Lett., 27, 1047-1050 (1986).
R. T. Arnold et al., "Activated Metals. A Procedure for the Preparation of Activated Magnesium and Zinc", Synthetic Communications, 7, 223-232 (1977).
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).
S. C. Berk et al., "General Approach to Highly Functionalized Benzylic Organometallics of Zinc and Copper," J. Org. Chem., 53, 5789-5791 (1988).
A. V. Bogat-skii et al., "Calcium-Containing Organic Compounds. II. Preparation of Organocalcium Compounds and Study of Their Properties," Zhurnal Obschei Khimii, 47, 2297-2305 (1977) (with English translation).
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).
T.--A. Chen et al., "The First Regioregular Head-to-Tail Poly(3-hexylthiophene-2,5-diyl) and a Regiorandom Isopolymer: Ni vs. Pd Catalysis of 2(5)-Bromo-5(2)-(bromozincio)-3-hexylthiophene Polymerization," J. Am. Chem. Soc., 114, 10087-10088 (1992).
E. J. Corey et al., "The Reactions of Combined Organo-cuprate-Chlorotrimethylsilane Reagents with Conjugated Carbonyl Compounds," Tetrahedron Lett., 26, 6019-6022 (1985).
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).
G. W. Ebert et al., "Preparation of Aryl, Alkynyl, and Vinyl Organocopper Compounds by the Oxidative Addition of Zerovalent Copper to Carbon-Halogen Bonds," J. Org. Chem., 53, 4482-4488 (1988).
E. Erdik, "Copper(I) Catalyzed Reactions of Organolithiums and Grignard Reagents," Tetrahedron, 40, 641-657 (1984).
G. Erker et al., "The Remarkable Features of (.sup.4 -Conjugated Diene) zirconocene and --hafnocene Complexes," Adv. Organomet. Chem., 24, 1-39 (1985).
L. F. Fieser et al., "Synthesis of Keto Acids by Chromic Anhydride Oxidation of Tertiary Alcohols," J. Am. Chem. Soc., 70, 3352-3355 (1948).
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. G. Gowenlock et al., "The Organometallic Chemistry of the Alkaline Earth Metals," J. Organomet. Chem. Library, Organomet. Chem. Rev., 3, 1-73 (1977).
T. P. Hanusa, "New Developments in the Organometallic Chemistry of Calcium, Strontium and Barium," Polyhedron, 9, 1345-1362 (1990).
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).
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. Itsuno et al., "The First Direct Formation of a Grignard Reagent on an Insoluble Polymer," J. Org. Chem., 52, 464-4645 (1987).
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).
N. Kawabata et al., "Preparation of Organocalcium Halides," Tetrahedron, 29, 1069-1071 (1973).
N. Kawabata et al., "Preparation of Organocalcium Halides in Hydrocarbon Solvents," J. Org. Chem., 38, 4268-4270 (1973).
D. W. Knight, "Saturated Carbocyclic Ring Synthesis," Gen. Synth. Methods, 6, 277-(1983).
H. Kroto, "C.sub.60 fullerenes, giant fullerenes and soot," Pure & Appl. Chem., 62, 407-415 (1990).
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).
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).
M. J. McCormick et al., "Preparation of Activated Calcium, Strontium, and Barium Powders by Reduction of Alkaline Earth Di-iodides," J.C.S., Chem. Commun., 778-779 (1990).
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 Syntheses," Pure & Appl. Chem., 53, 2333-2356 (1981).
R. A. O'Brien et al., "Direct Metalation of p-Bromopolystyrene Using Highly Reactive Copper and Prepation and Reaction of Highly Reactive Copper Bound to an Insoluble Polymer," J. Org. Chem., 55, 788-90 (1990).
R. A. O'Brien et al., "Chemical Modification of Halogenated Polystyrene Resins Utilizing Highly Reactive Calcium and the Formation of Calcium Cuprate Reagents in the Preparation of Functionalized Polymers," J. Org. Chem., 57, 2667-2677 (1992).
R. A. O'Brien et al., "Functionalization of Halogenated Polystyrene Resins Utilizing Highly Reactive Calcium," J. Inorg. & Organomet. Poly., 2, 345-356 (1992).
R. A. O'Brien, "Chemical Modification of Halogenated Polystyrene Resins Utilizing Highly Reactive Copper and Calcium and the Chemistry of Highly Reactive Copper Contained in a Polymer", Abstract of Ph.D. Thesis (1992), The

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