WO1997024300A1 - Couplage croise de composes organiques a l'aide d'iodure cuivreux - Google Patents

Couplage croise de composes organiques a l'aide d'iodure cuivreux Download PDF

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Publication number
WO1997024300A1
WO1997024300A1 PCT/US1996/020564 US9620564W WO9724300A1 WO 1997024300 A1 WO1997024300 A1 WO 1997024300A1 US 9620564 W US9620564 W US 9620564W WO 9724300 A1 WO9724300 A1 WO 9724300A1
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WO
WIPO (PCT)
Prior art keywords
substituted
alkenyl
aralkyl
aryl
alkyl
Prior art date
Application number
PCT/US1996/020564
Other languages
English (en)
Inventor
Reuben D. Rieke
Original Assignee
Rieke Metals, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/701,628 external-priority patent/US5852200A/en
Application filed by Rieke Metals, Inc. filed Critical Rieke Metals, Inc.
Publication of WO1997024300A1 publication Critical patent/WO1997024300A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/02—Addition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/004—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with organometalhalides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation

Definitions

  • This invention is directed to the use of cuprous iodide to catalyze the reaction of organozinc compounds with various organic compounds, including acid halides, allylic halides, and ⁇ , ⁇ -unsaturated carbonyls.
  • the invention provides a method of coupling a carboxylic acid halide and an organozinc compound, the method comprising reacting the carboxylic acid halide with the organozinc compound in the presence of cuprous iodide (Cul) .
  • the invention also provides a method of coupling an allylic halide and an organozinc compound, the method comprising reacting the allylic halide with the organozinc compound in the presence of cuprous iodide.
  • the invention further provides a method of adding an organozinc compound to an ⁇ , ⁇ -unsaturated carbonyl containing compound, the method comprising reacting the organozinc compound with the ⁇ , ⁇ -unsaturated carbonyl containing compound in the presence of cuprous iodide.
  • alkyl and alkylene are inclusive of acyclic and cyclic straight and branched chain alkyl and alkylene groups.
  • aryl as used herein is inclusive of single and polycyclic hydrocarbyl aromatic and heteroaromatic groups. Examples of aryl groups include benzene, naphthalene, pyridine, thiophene, furan, and the like.
  • ⁇ , ⁇ -unsaturated carbonyl containing compound is inclusive of ⁇ , ⁇ -unsaturated ketones as well as other compounds containing ⁇ , ⁇ -unsaturated carbonyl functionality. Examples of such compounds include ⁇ , ⁇ -unsaturated aldehydes, amides, esters, and the like.
  • substituted as applied to any substituent group includes those groups that are substituted by a non-hydrogen substituent group.
  • groups include, for example, hydrogen, hydroxy, alkyl, alkenyl, alkoxy, aryl, aralkyl, aralkenyl, ether, amino, alkylamino, dialkylamino, carboxylic acyl, carboxylic acid ester, carbamoyl, carbamate, nitrile, oxo, and ketone groups.
  • the invention provides methods of coupling various organic compounds, including acid halides, allylic halides, and ⁇ , ⁇ -unsaturated carbonyl containing compounds, with organozinc compounds by using Cul as a catalyst.
  • organozinc compounds including acid halides, allylic halides, and ⁇ , ⁇ -unsaturated carbonyl containing compounds
  • organozinc compound may be used in the method of the invention, including functionalized and/or substituted organozinc compounds.
  • organozinc compounds include organozinc compounds of formula (1) :
  • organozinc compounds include those wherein X is I, Cl or Br, and R is a substituted alkyl, substituted alkenyl, substituted aryl, substituted aralkyl, or substituted aralkenyl group.
  • the organozinc compounds useful in the method of the invention may be prepared by methods known to those of skill in the art, including those described by Rieke in U.S. Patent No. 5,358,546, the disclosure of which is incorporated herein by reference.
  • Cuprous iodide is a well known and readily available catalyst.
  • the Cul may be used alone or in combination with another reagent if desired, for example to increase the solubility of the Cul in the chosen solvent.
  • Cul alone is insoluble in THF, but if a molar proportion of a lithium halide such as LiBr, LiCl or Lil equal to the molar proportion of Cul present is added, a majority of the Cul dissolves in the THF. While the invention is not bound by any theory of operation, it is believed that a complex of Cul and the lithium halide is formed and that this complex can also function to catalyze cross-coupling and addition reactions between organozinc compounds and organic compounds.
  • An effective amount of the Cul catalyst is present in the reaction mixture to allow the cross-coupling or addition reaction to proceed to completion. Typically, this is about 0.0001 to 1.0 moles of Cul per mole of organozinc compound used, with about 0.05 to 0.10 moles Cul per mole of organozinc compound preferred.
  • R and X are as described supra, X' is a halogen atom and Rl represents a non-aldehyde containing organic radical.
  • X is I, Br or Cl and Rl is selected from the group consisting of alkyl, substituted alkyl, alkenyl, substituted alkenyl, amino, substituted amino, aryl, aralkyl, aralkenyl, substituted aryl, substituted aralkyl, and substituted aralkenyl.
  • X is Br
  • X' is Cl or Br
  • R and Rl are independently selected from the group consisting of substituted alkyl, substituted alkenyl, substituted aryl, substituted aralkyl, and substituted aralkenyl.
  • the Cul catalyzed coupling reaction between the organozinc compound and the acid halide is preferably carried out in an organic solvent. Any organic solvent which will not interfere with the reaction may be used.
  • Suitable types of organic solvents include, for example, alcohols, hydrocarbons having about 4 to 80 carbon atoms, ethers, ketones, and the like.
  • Preferred solvents include dimethoxyethane, dioxane, diethoxymethane, ethylene glycol dibutyl ether, and THF, with THF especially preferred.
  • the Cul and if desired the lithium halide is placed into a suitable reaction vessel along with the organozinc compound and solvent.
  • the reaction is preferably carried out under an inert atmosphere, such as argon or nitrogen.
  • the mixture is stirred until uniform and cooled to a temperature of about -100°C to room temperature (about 25°C) , preferably to about -40°C to -20°C.
  • the acid halide is added.
  • the addition may be accomplished in any known manner. Generally, the molar ratio of organozinc compound to acid halide is about 2:1 to 1:3, with 1:0.8 preferred.
  • the reaction mixture is stirred typically for about 5 to 300 minutes, preferably about 20 to 30 minutes. At this point the reaction is complete and the product may be allowed to warm to room temperature if desired.
  • the product may be used as is or isolated.
  • reaction scheme (la) One particular type of reaction of an organozinc compound with an acid halide provides a new synthetic route to the preparation of functionalized benzil molecules.
  • aryl or substituted aryl organozinc compounds can be reacted with oxalyl chloride or oxalyl bromide in the presence of Cul.
  • Such reactions generally follow reaction scheme (la) :
  • Ar is an unsubstituted or substituted benzene group, and most preferably Ar is a substituted benzene group.
  • X' is preferably Cl or Br.
  • the Cul and lithium halide if a lithium halide is used, is placed in a reaction vessel under an inert atmosphere.
  • the organic solvent is added with stirring and the temperature of the mixture adjusted to about -100°C to room temperature (about 25°C), preferably to about -40°C to -20°C.
  • the organozinc compound is then added and stirring continued.
  • the oxalyl halide is added and if at a reduced temperature the reaction mixture allowed to come to room temperature while stirring continues.
  • the product may be isolated or used directly.
  • R2 is selected from the group consisting of H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, aralkyl, aralkenyl, substituted aryl, substituted aralkyl, and substituted aralkenyl
  • R3 is selected from the group consisting of alkyl substituted alkyl, alkenyl, substituted alkenyl, aryl, aralkyl, aralkenyl substituted aryl, substituted aralkyl and substituted aralkenyl.
  • R2 and R3 are independently selected from the group consisting of substituted alkyl, substituted alkenyl, substituted aryl, substituted aralkyl, and substituted aralkenyl.
  • the Cul and lithium halide if used, are placed into a suitable reaction vessel along with the organozinc compound and solvent.
  • the solvent is preferably in organic solvent as described supra. This reaction is preferably carried out under an inert atmosphere, such as argon or nitrogen. The mixture is stirred until uniform and the temperature adjusted to about -100°C to room temperature (about 25°C), preferably about -40°C to -20°C.
  • the allyl halide is added.
  • the addition may be accomplished in any known manner. Generally, the molar ratio of organozinc compound to allylic halide ranges from about 3:1 to 1:3, with a 1:1 ratio preferred.
  • This reaction mixture is stirred for about 5 to 300 minutes, preferably about 20 to 30 minutes. If cooled, the reaction mixture may be maintained at the reduced temperature or allowed to rise freely to room temperature. When the reaction is complete the product is worked up using a method known in the art. Yields for this reaction are typically about 90 to 98%.
  • R4 and R5 are independently selected from the group consisting of H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, amino, substituted amino, alkoxy, substituted alkoxy, aryl, aralkyl, aralkenyl substituted aryl, substituted aralkyl, and substituted aralkenyl, or R4 and R5 together form a -(CH 2 ) n - group, wherein n is 2 to 4; and R6 is selected from the group consisting of alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, amino, substituted amino, alkoxy, substituted alkoxy, aralkyl, substituted aralkyl, aralkenyl, and substituted aralkenyl.
  • R4, R5 and R6 are independently selected from the group consisting of substituted alkyl, substituted alkenyl, substituted amino, substituted alkoxy, substituted aryl, substituted aralkyl, and substituted aralkenyl.
  • Cul and lithium halide, if used, along with the desired solvent are placed in a reaction vessel.
  • the organozinc reagent is then added to the vessel.
  • the reaction is preferably carried out under an inert atmosphere, such as argon or nitrogen.
  • the mixture is stirred until uniform and the temperature adjusted to about -100°C to room temperature (about 25°C) , preferably about -40°C to -20°C.
  • the enone compound When the mixture is cooled, the enone compound is added to the reaction vessel. To improve the yield of this reaction, BF 3 and Si(CH 3 ) 3 Cl are also present. They are generally added to the reaction vessel at the same time as the enone compound. Generally, the molar ratio of organozinc compound to enone ranges from about 1:1 to 3:0.5, with 1:0.7 preferred. For any given proportion of organozinc compound to enone, BF 3 is present in an amount of about 0.1 to 5.0 moles, preferably about 1.5 moles, and Si (CH 3 ) 3 C1 is present in an amount ranging from about 0.1 moles to 5.0 moles, preferably about 2.0 moles.
  • reaction mixture is stirred for about 5 to 300 minutes, preferably about 20 to 30 minutes. During this time the reaction mixture, if cooled, may be maintained at a reduced temperature or allowed to rise to room temperature. When the reaction is complete the product may be used as is or worked up in a manner known in the art .
  • the invention is further described by reference to the following examples, which are understood to be illustrative and not limiting of the invention.
  • RZnX This organozinc was not freshly prepared but was prepared in 4/93 and 11/94. Coupling of RZnX: The same procedure as before was followed except 4-Bromobenzoyl chloride, 35.0 grams (0.16 mol) dissolved in 10 mL THF was used. After stirring 3 h from -40°C to room temperature the reaction product was worked up by adding hot hexanes to the resulting solid until it went into solution, cooled to room temperature slowly and placed into the freezer. A very pure looking white solid was obtained. The hexanes were drained off, providing a yield of 75% of product having a melting point of 44-46°C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Le couplage croisé ou les réactions d'addition de composés organiques, notamment des halogénures d'acide, des halogénures allyliques, et de composés contenant du carbonyle $(g)a, β-insaturé, avec des composés organozinciques peuvent s'effectuer aisément et sans danger en présence d'iodure cuivreux. L'emploi de ce catalyseur dans la réaction de couplage permet la préparation de produits d'utilité commerciale dans les industries pharmaceutique, agrochimique et autres.
PCT/US1996/020564 1995-12-28 1996-12-18 Couplage croise de composes organiques a l'aide d'iodure cuivreux WO1997024300A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US933095P 1995-12-28 1995-12-28
US60/009,330 1995-12-28
US08/701,628 US5852200A (en) 1996-08-22 1996-08-22 Cross-coupling of organic compounds using cuprous iodide
US08/701,628 1996-08-22

Publications (1)

Publication Number Publication Date
WO1997024300A1 true WO1997024300A1 (fr) 1997-07-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101196689B1 (ko) * 2007-06-20 2012-11-08 로디아 오퍼레이션스 복합 폴리아미드 물품

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5358546A (en) * 1992-02-04 1994-10-25 Board Of Regents Of The University Of Nebraska Highly reactive forms of zinc and reagents thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5358546A (en) * 1992-02-04 1994-10-25 Board Of Regents Of The University Of Nebraska Highly reactive forms of zinc and reagents thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
E. NAKAMURA: "Copper-catalyzed acylation and conjugate addition of zinc homoenolate. Synthesis of 4- and 6-oxo esters.", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 106, no. 11, 30 May 1984 (1984-05-30), DC US, pages 3368 - 3370, XP002030288 *
M. V. HANSON: "Direct formation of secondary and tertiary alkylzinc bromides", TETRAHEDRON LETTERS, vol. 35, no. 39, 26 September 1994 (1994-09-26), OXFORD GB, pages 7205 - 7208, XP000465075 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101196689B1 (ko) * 2007-06-20 2012-11-08 로디아 오퍼레이션스 복합 폴리아미드 물품

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