US2015259284A1PendingUtilityA1

Process for preparing aminocyclohexyl ether compounds

Assignee: CARDIOME INTERNAT AGPriority: Aug 16, 2010Filed: Mar 19, 2015Published: Sep 17, 2015
Est. expiryAug 16, 2030(~4.1 yrs left)· nominal 20-yr term from priority
C12P 17/10C07D 207/12C07D 207/416C07C 217/52
46
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Claims

Abstract

The present invention relates to a process for preparing aminocyclohexyl ether compounds of Formula I: or the pharmaceutically acceptable salts and esters thereof. In particular, the instant invention is directed towards a process for preparing (1R,2R)-2-[(3R)-Hydroxypyrrolidinyl]-1-(3,4-dimethoxyphenethoxy)-cyclohexane as well as various intermediates.

Claims

exact text as granted — not AI-modified
1 . A process for preparing compounds of Formula I: 
       
         
           
           
               
               
           
         
       
       where Y is selected from 3,4-dimethoxyphenyl, 3,4-dihydroxyphenyl or a 3,4-dihalophenyl, comprising the steps of:
 a) mixing a cyclohexyl amine (iv) 
 
       
         
           
           
               
               
           
         
       
       with a malic acid derivative (v) 
       
         
           
           
               
               
           
         
       
       where R 2  is selected from hydrogen, esters, carbonates, carbamates, silyl ethers, phosphates or sulfates and where X and Z are independently selected from OH C 1 -C 6  alkoxy, esters, halides or O-acyl, said X and Z may optionally be joined to form a ring (v-a) 
       
         
           
           
               
               
           
         
       
       to obtain a hydroxy succinimide (vi) 
       
         
           
           
               
               
           
         
       
       and
 b) reducing the hydroxy succinimide (vi) to obtain a compound of Formula I. 
 
     
     
         2 - 19 . (canceled) 
     
     
         20 . A D-malate salt of 
       
         
           
           
               
               
           
         
       
     
     
         21 . The salt of  claim 20  which is in crystalline form. 
     
     
         22 . The crystalline salt of 
       
         
           
           
               
               
           
         
       
       of  claim 21  characterized as by characteristic absorption bands obtained from the X-ray powder diffraction pattern at spectral d-spacings of 5.38, 9.41, 19.43 and 7.18 angstroms. 
     
     
         23 . The crystalline salt of 
       
         
           
           
               
               
           
         
       
       of  claim 21  further characterized by the X-ray powder diffraction pattern of  FIG. 1 . 
     
     
         24 . A process for preparing compounds of Formula I: 
       
         
           
           
               
               
           
         
       
       where Y is selected from 3,4-dimethoxyphenyl, 3,4-dihydroxyphenyl or a 3,4-dihalophenyl, comprising the step of:
 a) adding a cyclohexyl amine salt (iv-a) 
 
       
         
           
           
               
               
           
         
       
       to a mixture of a second solvent and an inorganic base followed by addition of a 1,4-dielectrophile of formula vii-a or vii-b 
       
         
           
           
               
               
           
         
       
       where R 2  is selected from hydrogen, esters, carbonates, carbamates, silyl ethers, phosphates or sulfates and X is an activated leaving group, to provide a mixture comprising the compound of Formula (I). 
     
     
         25 . The process of  claim 24  further comprising the steps:
 b) adding a second solvent and a basic aqueous solution to the mixture, to thereby obtain a biphasic mixture of an aqueous layer and an organic layer; 
 c) discarding the aqueous layer; and 
 d) adding an acid to the organic layer to obtain a salt of a compound of Formula (I). 
 
     
     
         26 . The process of  claim 24  wherein the activated leaving group X is selected from the group consisting of chloride, bromide, iodide, mesylate, tosylate, and triflate. 
     
     
         27 . The process of  claim 24  wherein the 1,4-dielectrophile is a compound of formula vii-a where R2 is hydrogen and X is bromide, mesylate or tosylate. 
     
     
         28 . The process of  claim 24  wherein the 1,4-dielectrophile is a compound of formula vii-b. 
     
     
         28 . The process of  claim 24  wherein the 1,4-dielectrophile is (R)-1,4-dibromo-butan-2-ol. 
     
     
         29 . The process of  claim 25  further comprising:
 e) mixing a substituted ethanol (ii) 
 
       
         
           
           
               
               
           
         
       
       where Y is selected from 3, 4-dimethoxyphenyl, 3,4-dihydroxyphenyl or 3,4-dihalophenyl, with a zinc salt, a secondary amine and an organic base in a first solvent;
 f) adding a substituted cycloalkanone (i) 
 
       
         
           
           
               
               
           
         
       
       where R1 is an activated leaving group and integer n is 2, to obtain a mixture;
 g) adding an acidic aqueous solution to create a biphasic mixture and discarding the aqueous layer; 
 h) adding a second solvent to obtain an alkoxy ketone (iii) 
 
       
         
           
           
               
               
           
         
         i) mixing a co-factor with a slurry of a transaminase polypeptide in a basic buffer and an amine to produce a solution; 
         j) adding the alkoxy ketone (iii) 
       
       
         
           
           
               
               
           
         
         k) adding a third solvent to create a biphasic mixture and discarding the aqueous layer; 
         l) performing a solvent switch from the third solvent to a fourth solvent to obtain cyclohexyl amine (iv) 
       
       
         
           
           
               
               
           
         
         m) adding an acid to create a slurry; and 
         n) filtering the slurry to obtain the cyclohexyl amine salt (iv-a). 
       
     
     
         30 . The process of  claim 29 , where a transaminase polypeptide having an amino acid sequence of SEQ ID NO: 18 or SEQ ID NO: 206 is used. 
     
     
         31 . The process of  claim 29 , where a transaminase polypeptide having a polynucleotide sequence of SEQ ID NO: 17 or SEQ ID NO: 205 is used. 
     
     
         32 . A process for preparing compounds of Formula I: 
       
         
           
           
               
               
           
         
       
       where Y is selected from 3,4-dimethoxyphenyl, 3,4-dihydroxyphenyl or a 3,4-dihalophenyl, comprising the step of:
 o) mixing an alkoxy ketone (iii) 
 
       
         
           
           
               
               
           
         
       
       where Y is selected from 3,4-dimethoxyphenyl, 3,4-dihydroxyphenyl or a 3,4-dihalophenyl, with a co-factor, a transaminase polypeptide and an amine to produce a cyclohexyl amine (iv) 
       
         
           
           
               
               
           
         
       
     
     
         33 . The process of  claim 32  further comprising mixing the cyclohexyl amine (iv) with an inorganic or organic protic acid, HW, to provide a salt of the formula 
       
         
           
           
               
               
           
         
       
     
     
         34 . The process of  claim 33  wherein HW is selected from HCl, H2SO4, oxalic acid, pivalic acid, malic acid and maleic acid. 
     
     
         35 . The process of claim  11  wherein HW is maleic acid and the salt 
       
         
           
           
               
               
           
         
       
       form has the formula (iv-a) 
       
         
           
           
               
               
           
         
       
     
     
         36 . The process of  claim 33  wherein HW is oxalic acid and the salt form has the formula (iv-b) 
       
         
           
           
               
               
           
         
       
     
     
         37 . The process of  claim 33  wherein HW is malic acid and the salt form has the formula (iv-c) 
       
         
           
           
               
               
           
         
       
     
     
         38 . The process of  claim 32 , where a transaminase polypeptide having an amino acid sequence of SEQ ID NO: 18 or SEQ ID NO: 206 is used. 
     
     
         39 . The process of  claim 32 , where a transaminase polypeptide having a polynucleotide sequence of SEQ ID NO: 17 or SEQ ID NO: 205 is used.

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