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(12) Patent Application Publication (10) Pub. No.: US 2003/0220520 A1 Marcuccio Et Al US 2003O220520A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2003/0220520 A1 Marcuccio et al. (43) Pub. Date: Nov. 27, 2003 (54) PROCESS FOR PREPARING ORGANIC Related U.S. Application Data BORONIC ACID DERVATIVES USING DIBORONIC ACID (62) Division of application No. 10/103,708, filed on Mar. 25, 2002, now Pat. No. 6,603,004, which is a division (75) Inventors: Sebastian Mario Marcuccio, of application No. 09/486,696, filed on May 10, 2000, Endeavour Hills (AU); Mary now Pat. No. 6,448,433, filed as 371 of international Rodopoulos, Blackburn South (AU); application No. PCT/AU98/00726, filed on Sep. 8, Helmut Weigold, Mount Waverley 1998. (AU) (30) Foreign Application Priority Data Correspondence Address: BACON & THOMAS, PLLC Sep. 8, 1997 (AU)............................................ PO 9038 625 SLATERS LANE FOURTH FLOOR Publication Classification ALEXANDRIA, VA 22314 (51) Int. Cl." ................................. C07F 5/02; CO8F 8/42 (73) Assignee: Commonwealth Scientific and Indus (52) U.S. Cl. ................................................. 562/7; 525/337 trial Research Organisation, Campbell (57) ABSTRACT (AU) The invention relates to a proceSS for the preparation of (21) Appl. No.: 10/460,616 organic boronic acid derivatives involving the reaction of an organic compound with diboronic acid in the presence of a (22) Filed: Jun. 13, 2003 Group 8-11 metal catalyst. US 2003/0220520 A1 Nov. 27, 2003 PROCESS FOR PREPARING ORGANIC BORONIC is Stable in refluxing methanol, ethanol, isopropyl alcohol or ACID DERIVATIVES USING DIBORONIC ACID t-butyl alcohol and is not cleaved by cold water. The dehydrated form is Soluble in methanol at room temperature, 0001. The present invention relates to a method for dissolves rapidly in ethanol or isopropanol on warming, and preparing boron derivatives of organic compounds, in par in t-butyl alcohol at 82 C. (A. L. McClosky, R. J. Broth ticular to boronic acid derivatives of organic compounds. erton & J. L. Boone, J Am Chem. Soc. 1961 83 4750) 0002 Boronic acid derivatives of organic compounds are of particular interest, not only as intermediary means for 0011 AS used herein, the term “diboronic acid” refers to forming covalent carbon-carbon bonds between organic (HO), B-B(OH) or its dehydration product; and compounds, but as a starting point for further chemical 0012 the term “boronic acid residue” refers to the group manipulations and transformations or in conferring or -B(OH). increasing biological activity to otherwise biologically inac tive compounds. 0013 The term “organic boronic acid derivative” refers to an organic compound having a boronic acid residue at a 0003) Whilst these boronic acid derivatives may be Substitution position. obtained by conventional hydrolysis or hydrogenolysis pro cedures applied to boronic ester compounds, many conven 0014. The term “boron reactive site' as used herein refers tional conditions employed in the preparation of boronic to any carbon atom within a molecule capable of reacting ester compounds are incompatible with compounds bearing with diboronic acid in the presence of a Group 8-11 metal Sensitive functionalities. Furthermore, there are practical catalyst to provide a boronic acid residue on that carbon and commercial advantages in reducing the number of atom. Examples of boron reactive Sites include carbon atoms chemical manipulations employed in a Synthetic procedure having halogen or halogen-like Substituents, carbon atoms and it is therefore desirable to obtain the boronic acid taking part in carbon to carbon double or triple bonds, and carbon atoms in an allylic position having a Substituent derivatives directly. leaving group. 0004. It has now surprisingly been found that diboronic acid can be reacted in the presence of a Group 8-11 metal 0015. It has been found, in particular, that when an catalyst with an organic compound under mild conditions to organic compound having a halogen or halogen-like Sub provide boronic acid derivatives directly, thereby circum Stituent is reacted with diboronic acid in the presence of a venting the hydrolysis or hydrogenolysis Step and allowing Group 8-11 metal catalyst and a Suitable base, the halogen for the presence of Sensitive functional groups. or halogen-like Substituent on the organic compound can be replaced by a boronic acid residue. 0005 Accordingly, the present invention provides the use of diboronic acid in the preparation of organic boronic acid 0016. Accordingly, in one embodiment of the invention, derivatives containing at least one boronic acid residue. there is provided a process for preparing organic boronic acid derivatives which comprises reacting an organic com 0006 The invention further provides a process for pre pound having a halogen or halogen-like Substituent at a paring organic boronic acid derivatives comprising reacting Substitution position with diboronic acid in the presence of an organic compound having a boron reactive site with a Group 8-11 metal catalyst and a Suitable base Such that the diboronic acid in the presence of a Group 8-11 metal halogen or halogen-like Substituent is Substituted with a catalyst. boronic acid residue. 0007. The use of diboronic acid offers a convenient and 0017 AS used herein, the term “organic compound hav advantageous means of introducing a boronic acid residue ing a halogen or halogen-like Substituent at a Substitution into an organic compound over conventional reagents. Its position” refers to any organic compound having a carbon to Stability towards water and oxygen under ambient condi halogen or carbon to halogen-like Substituent bond at a tions provides for ease of use when compared with other position at which Substitution by a boronic acid residue is reactive and Sensitive reagents used to make boronic acids desired. The organic compound may be aliphatic, olefinic, via the esters, which require a strictly controlled environ acetylenic, aromatic, polymeric, dendritic, cyclic or any ment. combination thereof. The compound may further comprise 0008. In the preparation of organic boronic acids, the use additional heteroatoms Such as Sulfur, oxygen, nitrogen, of diboronic acid affords a number of advantages over that phosphorous, boron, Silicon, arsenic, Selenium, and tellu of diboronic acid esters. Firstly, diboronic acid itself is U. readily prepared from tetra(dimethylamino)diboron. Sec 0018 The terms “aromatic” and “aromatic compound(s)” ondly, the need for a hydrolysis or hydrogenolysis Step is as used herein refer to any compound which includes or circumvented as the boronic acid is the primary reaction consists of one or more aromatic rings. The aromatic rings product. Thirdly, by avoiding a hydrolysis or hydrogenolysis may be carbocyclic, or heterocyclic, and may be mono or Step, the formation of alcoholic by-products in the reaction polycyclic ring Systems. Examples of Suitable rings include mixture is eliminated. but are not limited to benzene, biphenyl, terphenyl, quater 0009 Diboronic acid can be dehydrated (TWartik and E. phenyl, naphthalene, tetradyronaphthalene, 1-benzylnaph F. Apple J Am. Chem. Soc. 1955 77 6400; 1958 80 6155). thalene, anthracene, dihydroanthracene, benzanthracene, dibenzanthracene, phenanthracene, perylene, pyridine, 4-phenylpyridine, 3-phenylpyridine, thiophene, ben 0010. It has now been found that the dehydrated form of Zothiophene, naphthothiophene, thianthrene, furan, pyrene, diboronic acid can also be used to prepare boronic acid isobenzofuram, chromene, Xanthene, phenoxathiin, pyrrole, derivatives. The boron to boron bond of the dehydrated form imidazole, pyrazole, pyrazine, pyrimidine, pyridazine, US 2003/0220520 A1 Nov. 27, 2003 indole, indolizine, isolindole, purine, quinoline, isoquinoline, preferred that the Substitution position is at a vinylic posi phthalazine, quinoxaline, quinazoline, quinoline, pteridine, tion. If the organic compound is a polymer or a dendrimer carbazole, carboline, phenanthridine, acridine, phenanthro it may have many Substitution positions. line, phenazine, isothiazole, isooxazole, phenoxazine and 0023. In this specification “optionally substituted” means the like, each of which may be optionally substituted. The that a group may or may not be Substituted with one or more terms “aromatic' and “aromatic compound(s)' include mol groupS Selected from alkyl, alkenyl, alkynyl, aryl, halo, ecules, and macromolecules, Such as polymers, copolymers haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, and dendrimers which include or consist of one or more alkoxy, alkenyloxy, aryloxy, benzyloxy, haloalkoxy, aromatic rings. The term "pseudoaromatic' refers to a ring haloalkenyloxy, haloaryloxy, isocyano, cyano, formyl, car system which is not strictly aromatic, but which is stabilized boxyl, nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, by means of delocalization of TL electrons and behaves in a nitroheterocyclyl, amino, alkylamino, dialkylamino, alkeny Similar manner to aromatic rings. Examples of pseudoaro lamino, alkynylamino, arylamino, diarylamino, benzy matic rings include but are not limited to furan, thiophene, lamino, imino, alkylimine, alkenylimine, alkynylimino, pyrrole and the like. arylimino, benzylimino, dibenzylamino, acyl, alkenylacyl, 0019. The term “olefinic compound” and “olefinic alkynylacyl, arylacyl, acylamino, diacylamino, acyloxy, organic compound” as used herein refers to any organic alkyl Sulphonyloxy, arylsulphenyloxy, heterocyclyl, hetero compound having at least one carbon to carbon double bond cycloxy,
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