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(12) United States Patent (10) Patent No.: US 7,973,171 B2 Burkhardt Et Al

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(12) United States Patent (10) Patent No.: US 7,973,171 B2 Burkhardt Et Al US007973 171B2 (12) United States Patent (10) Patent No.: US 7,973,171 B2 Burkhardt et al. (45) Date of Patent: Jul. 5, 2011 (54) PROCESS FOR SYNTHESIS OF OTHER PUBLICATIONS DALKOXYORGANOBORANES Beckman, et al., “Ring Strain in Boroxine Rings: Computational and Experimental Considerations”, Journal of Organometallic Chemis (76) Inventors: Elizabeth Burkhardt, Bridgeville, PA try, vol. 633, No. 1-2, pp. 149 to 156, 2001. (US); William Atkins, Evans-City, PA Dahlhoff, et al., “Boron Compounds. 45." 6-Deoxy-O-Acyl-Alpha (US) L-Mannofuranoses Via O-Ethylboranediyl Derivatives”. J. Org. Chem., vol. 42, No. 19, pp. 3151 to 3157, 1977. (*) Notice: Subject to any disclaimer, the term of this Brown, et al. “Organoboranes. 31. A Simple Preparation of Boronic Esters From Organolithium Reagents and Selected patent is extended or adjusted under 35 Trialkoxyboranes'. Organometallics, vol. 2, pp. 1316 to 1319, 1983. U.S.C. 154(b) by 0 days. Corey, et al., “Reduction of Carbonyl Compounds With Chiral Oxazaborolidine Catalysts: a New Paradigm for Enantioselective (21) Appl. No.: 12/947.238 Catalysis and a Powerful New Synthetic Method”. Angew. Chem. Int. Ed., vol. 37, pp. 1986 to 2012, 1998. (22) Filed: Nov. 16, 2010 Miyaura, et al., “Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds', Chem. Rev., vol. 95, pp. 2457 to 2483, (65) Prior Publication Data 1995. Brown, Herbert C., at al., “Organoboranes. 30. Convenient Proce US 2011 FOO6O163 A1 Mar. 10, 2011 dures for the Synthesis of Alkyl-And Alkenylboronic Acids and Esters'. Organometallics, vol. 2, pp. 1311 to 1316, 1983. Related U.S. Application Data Dahlhoff, et al., “Selective Syntheses of the Methyla-D-Furanosides of Lyxose and Mannose Using Ethyl(Dimethoxy) Borane'. Liebigs (62) Division of application No. 1 1/917,257, filed as Ann. Chem., vol. 8, pp. 807 to 810, 1990. application No. PCT/EP2006/063044 on Jun. 9, 2006, Corey, et al., “A New Process for the Generation of 1,3,2- now Pat. No. 7,858,827. Oxazaborolidines, Catalysts for Enantioselective Synthesis'. Tetra hedron Letters, vol. 33, No. 29, pp. 4140 to 4144, 1992. (60) Provisional application No. 60/690,113, filed on Jun. Chavant, et al., “Preparation of Some Organo-Bis 13, 2005. (Diisopropylamino) Boranes and Their Application to the Synthsis of Oxazaborolidines”, Journal of Organometallic Chemistry, vol. 455. (51) Int. C. pp. 37 to 46, 1993. C07D 207/00 (2006.01) CO7D 23/00 (2006.01) * cited by examiner (52) U.S. Cl. ........................................ 548/405; 548/110 Primary Examiner — Jafar Parsa (58) Field of Classification Search .................. 548/110, 548/405 (74) Attorney, Agent, or Firm — Connolly Bove Lodge & See application file for complete search history. Huitz LLP (57) ABSTRACT (56) References Cited The invention relates to a process for the synthesis of U.S. PATENT DOCUMENTS dialkoxyorganoboranes, in particular to a process for the Syn 3,027,396 A 3, 1962 Willcokson et al. thesis of dialkoxyorganoboranes by an ester exchange reac 3,203,928 A 8, 1965 Willcockson et al. tion. Moreover, the invention relates to a process for the 3,375,265 A 3/1968 Fetterly et al. synthesis of organo-oxazaborolidine catalysts (organo-CBS) 3,853,941 A 12/1974 Hough et al. 5,264,585 A 11/1993 Blacklocket al. and of trialkylboroxins. Furthermore, the invention relates to 5,463,131 A 10, 1995 Burkhardt methods of using dialkoxyorganoboranes for the preparation 6,037,505 A * 3/2000 Quallich ....................... 568,881 of organo-CBS catalysts and in Suzuki-type coupling reac tions. FOREIGN PATENT DOCUMENTS WO WO-02/22623 A1 3, 2002 2 Claims, No Drawings US 7,973,171 B2 1. 2 PROCESS FOR SYNTHESIS OF ranes for the synthesis of alkyl-CBS catalysts has also been DALKOXYORGANOBORANES described (Chavant, P. Y. et al., J. Organomet. Chem. 455, 37-46 (1993), but these are quite expensive reagents. RELATED APPLICATIONS It was one object of the present invention to provide a This application is a divisional application of U.S. patent simple and efficient process for the preparation of dialkoxy application Ser. No. 1 1/917,257, filed Dec. 12, 2007, which is organoboranes. The formation of water or other by-products, a national stage application (under 35 U.S.C. S371) of PCT that might be difficult to handle or to remove, should be Application No. PCT/EP2006/063044, filed Jun. 9, 2006, avoided during the process. It was another object of the which claims benefit of U.S. Provisional Patent Application 10 present invention to establish a process for the production of No. 60/690,113, filed Jun. 13, 2005. organo-oxazaborolidine catalysts (organo-CBS) using dialkoxyorganoboranes. In addition, a new and efficient FIELD OF THE INVENTION method for the preparation of trialkoxyboroxins should be developed. The invention relates to a process for the synthesis of 15 dialkoxyorganoboranes, in particular to a process for the Syn SUMMARY OF THE INVENTION thesis of dialkoxyorganoboranes by an ester exchange reac tion. Moreover, the invention relates to processes for the synthesis of organo-oxazaborolidine catalysts (organo-CBS) Accordingly, the present invention provides a novel pro and of trialkylboroxins. Furthermore, the invention relates to cess for the preparation of dialkoxyorganoboranes of the for methods of using dialkoxyorganoboranes for the preparation mula R'—B(OR), comprising the step of reacting a trior of organo-CBS catalysts and in Suzuki-type coupling reac ganoboroxin of the formula (R'—BO) with a trialkylborate tions. of the formula B(OR) (wherein R' and Rare defined here inafter). Furthermore, improved processes for the manufac BACKGROUND OF THE INVENTION ture of organo-CBS catalysts using dialkoxyorganoboranes 25 as starting material and of trialkoxyboroxins are disclosed. In Dialkoxyorganoboranes are versatile reagents for organic addition, new methods of using dialkoxyorganoboranes for syntheses and have for example been employed in so diverse the preparation of organo-CBS catalysts and in Suzuki-type fields as in the synthesis of antibiotics, insecticides and orga coupling reactions are provided. noborohydrides. Dialkoxymethylboranes can potentially be 30 used for the synthesis of methyl-substituted chiral oxazaboro DETAILED DESCRIPTION OF THE INVENTION lidines (known as MeCBS named after Corey, Bakshi and Shibata. c.f. Corey, E. J. et al., Angew. Chem. Int. Ed., 37, According to the invention the process for the synthesis of 1986-2012 (1998)), which are powerful enantioselective the dialkoxyorganoboranes (3) of the formula R'—B(OR), catalysts for ketone reductions. Another potential use for 35 dialkoxyorganoboranes is in Suzuki-type coupling reactions involves an ester exchange reaction between a triorga to introduce an organo group into a molecule under formation noboroxin (1) of the formula (R'—BO), and a trialkylborate of a new C. C-bond (Miyaura, N.; Suzuki, A., Chem Rev.95, (2) of the formula B(OR), wherein 2457-2483 (1995)). R" is C1-Cao alkyl, Cs-Co cycloalkyl, Co-C4 aryl, C7-C24 U.S. Pat. No. 5,463,131 describes the preparation of 40 aralkyl, C7-C2-alkaryl, C2-C20 alkenyl, Cs-C1s cycloalkenyl, dialkoxyalkylboranes by reacting excess trialkyborates with C-C alkynyl, CH2SiMe. Substituted C-C alkyl diborane in the presence of an olefin, e.g.: and R is C-Co alkyl, or two R groups in compounds 2 or 3 together with the Of course, dialkoxymethylboranes cannot be prepared by 45 —BO moiety form a cyclic structure of the formula that method. Another method for the manufacture of dialkoxyalkylbo ranes comprises esterification of alkylboronic acids (Brown, O H. C. et al., Organometallics 2(10), 1311-1316 (1983), 50 o B{ R Brown, H. C. et al., Organometallics 2010), 1316–1319 O (1983)) or trialkylboroxins (Dahlhoff, W. V. et al., Liebigs Ann. Chem. 8,807-810 (1990)) with an appropriate alcohol. with the divalent group R selected from the group consisting 55 (R-BO)+6ROH - - - is alkyl) CH or ortho-CH-alkyl Water is generated in these reactions, which very often disturbs further application of the product, even if only traces With R being a divalent group as defined above, the tri of water remain. 60 alkylborates (2) may have the following dinuclear structure: Water is especially detrimental to the function of the alkyl CBS catalysts, which can be prepared from dialkoxyalkylbo ranes. For this reason Corey proposed the use of bis(trifluo roethoxy)alkylboranes for the synthesis of ethyl- and n-butyl CBS derivatives to avoid the formation of water as a 65 by-product (Corey, E. J. et al., Tetrahedron Lett. 33(29), 4141-4144 (1992)). The use of bis(dialkylamino)alkylbo US 7,973,171 B2 3 4 the resulting dialkoxyorganoboranes (3) may have the fol c) separating the dialkoxymethylborane from the reaction lowing cyclic structure: mixture by distillation, wherein R is C-C alkyl or two R groups in compound (2) together with the —BO moiety form a cyclic structure of the formula O Preferred derivatives prepared by the process according to 10 —KOR the present invention are dialkoxyarganoboranes (3) of the O formula R'—B(OR), wherein R is methyl, ethyl, n-propyl, isopropyl or n-butyl and R is isopropyl or n-butyl. with the divalent group R selected from the group consisting The reaction is preferably performed under exclusion of air and moisture. The dialkoxyorganoborane (3) is preferably separated from the reaction mixture by distillation. The reac 15 tion is preferably carried out in the presence of at least one —(CH) , ortho-CH or ortho-CH-alkyl. non-coordinating solvent. Any non-coordinating solvent or According to another embodiment of the invention the mixtures thereof can be employed, preferably with a boiling synthesis of trialkoxyboroxins (4) of the formula (RO— point different (higher or lower) from that of the dialkoxyor BO) involves an ester exchange reaction between a triorga ganoborane (3) prepared in order to facilitate its easy separa noboroxin (1) of the formula (R'—BO), and a trialkylborate tion from the product.
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