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(12) United States Patent (10) Patent No.: US 6,437,171 B1 Karpf Et Al

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(12) United States Patent (10) Patent No.: US 6,437,171 B1 Karpf Et Al USOO6437171B1 (12) United States Patent (10) Patent No.: US 6,437,171 B1 Karpf et al. (45) Date of Patent: Aug. 20, 2002 (54) PROCESS FOR PREPARING 1,2-DIAMINO J.C. Rohloff, et al., J. Org. Chem. 1998, vol. 63, pp. COMPOUNDS 4545-4550. Green, T., Protective Groups in Organic Synthesis, Chapter (75) Inventors: Martin Karpf, Reinach; René 7, John Wiley & Sons, Inc. 1991, pp. 315–385. Trussardi, Birsfelden, both of (CH) M. Chini, et al., Tetrahedron Lett. 1994, vol. 35, pp. 433-436. (73) Assignee: Hoffman-La Roche Inc., Nutley, NJ P. Van de Weghe, Tetrahedron Lett. 1995, vol. 36, pp. (US) 1649-1652. Y. Yamamoto, J. Chem. Soc., Chem. Commun. 1993, pp. (*) Notice: Subject to any disclaimer, the term of this 1201-12O3. patent is extended or adjusted under 35 M. Caron, et al., J. Org. Chem. 1985, vol. 50, pp. U.S.C. 154(b) by 0 days. 1557-1560. Miller, et al., J. Org. Chem. 1998, vol. 63, pp.9753–9755. (21) Appl. No.: 09/590,317 Advanced Organic Chemistry, ed. March J. John Wiley & (22) Filed: Jun. 8, 2000 Sons, New York, 1992 pp. 353–357. Dobrev et al., Tetrahedron Letters, No. 39, pp. 4013-4016 (30) Foreign Application Priority Data (1972). Jun. 11, 1999 (EP) ............................................ 99.111418 Fulop et al., J. Org. Chem., vol. 58, pp. 1967–1969 (1969). Feb. 21, 2000 (EP) ............................................ OO103588 Abstract #164618y for C10. (51) Int. Cl." ..................... C07C 227/08; CO7C 247/14; * cited by examiner CO7D 317/44 (52) U.S. Cl. ....................... 560/125; 560/128; 560/169; Primary Examiner Ralph Gitomer 549/436; 549/546; 549/961 ASSistant Examiner-Devesh Khare (58) Field of Search ................................. 560/125, 128, (74) Attorney, Agent, or Firm--George W. Johnston; 560/169; 549/436,546,961 Dennis P. Tramaloni (57) ABSTRACT (56) References Cited The invention provides a multistep process for preparing U.S. PATENT DOCUMENTS 1,2-diamino compounds of formula 5,763.483. A 6/1998 Bischofberger et al. 5,859,284 A 1/1999 Kent et al. 5,866,601 A 2/1999 Lew et al. 1. 2 5,886.213 A 3/1999 Kent et al. 5,952.375 A 9/1999 Bischofberger et al. R1 R2 5,994,377. A 11/1999 Kim et al. RNR NH 6,057.459 A 5/2000 Kent et al. wherein R', R', R, R, R and R' have the meaning given FOREIGN PATENT DOCUMENTS in the Specification and pharmaceutically acceptable addi FR 1559511 * 3/1969 tion Salts thereof, from 1,2-epoxides of formula WO WO 96/26933 9/1996 WO WO 98/O7685 2/1998 II WO WO 98 O7685 * 2/1998 WO WO 99/14.185 3/1999 OTHER PUBLICATIONS Yamamoto et al. “Regio-and Stereo-Selective ring opening of epoxides with amide cuprate reagents.”, J. Chem. Soc., wherein R', R, R and R have the meaning given in the Chem. Commun. 1993, pp. 1201-1203.* Specification. C. U. Kim, et al., J. Am. Chem. Soc. 1997, vol. 119, pp. 681-690. 41 Claims, No Drawings US 6,437,171 B1 1 2 PROCESS FOR PREPARING 1,2-DIAMINO with the proviso that at least one of R', R', RandR is COMPOUNDS not H, and R and R", independently from each other, are H or a BACKGROUND OF THE INVENTION Substituent of an amino group, with the proviso that not The present invention concerns a new multi-step proceSS 5 both R and R', are H, for preparing 1,2-diamino compounds from 1,2-epoxides, in which process is characterized in that it comprises the Steps particular 1,2-diamino compounds useful as inhibitors of of Viral or bacterial neuraminidases, a new step of that multi a) reacting a 12-epoxide of formula Step process for preparing 2-aminoalcohols from 1,2- epoxides, a new Step for the transformation of a II 2-aminoalcohol into a 1,2-diamino compound as well as Specific intermediates useful in that multi-step process. PCT Patent Publication No. 96/26933 describes a large class of compounds useful as inhibitors of Viral or bacterial neuraminidases and their preparation. These compounds 15 wherein R', R', R and Rare as above with an amine comprise a six membered partially unsaturated carbocyclic of formula RNHR wherein R and R, independently of each other, are H, or a Substituent of an amino group, or heterocyclic ring System, which can be Substituted by with the proviso that not both R and Rare H to form several different Substituents. a 2-aminoalcohol of formula PCT Patent Publication No. 98/O7685 discloses various methods for preparing compounds of the above class which III are cyclohexene carboxylate derivatives. A particularly R R2 interesting compound is (3R,4R,5S)-5-amino-4- 1. 2 acetylamino-3-(1-ethyl-propoxy)-cyclohex-1-ene R1 e carboxylic acid ethyl ester (C. U. Kim et al., J. Am..Chem. OH RSNR6 Soc., 1997, 119, 681-690). A method of preparation of that 25 1,2-diamino compound in 10 Steps starting from Shikimic wherein R', R, R, R, R and R are as above acid, or in 12 StepS Starting from quinic acid, is described by b) converting the 2-aminoalcohol of formula (III) into a J. C. Rohloff et al., J. Org. Chem.,1998, 63,4545–4550. The 2-aminoalcohol of formula 10 Step method involves a final 4-step reaction Sequence IV from the 1,2-epoxide (1S,5R,6R)-5-(1-ethyl-propoxy)-7- R R2 oxa-bicyclo4.1.0hept-3-ene-3-carboxylic acid ethyl ester 1. 2 via three potentially highly toxic and explosive azide inter R1 R2 mediates. Dedicated know-how and expensive equipment OH NH are required to perform Such a proceSS. In a technical proceSS it is preferable to avoid use of azide reagents and azide 35 wherein R', R, R and R are as above, intermediates. c) transforming the 2-aminoalcohol of formula (IV) into The problem to be solved by the present invention there a 1,2-diamino compound of formula fore was to find an azide-free proceSS for preparing 1,2- diamino compounds from 1,2-epoxides. 40 That problem has been solved by the invention as 1. 2 described below and as defined in the appended claims. R1 R2 SUMMARY OF THE INVENTION NH RNR The invention provides a proceSS for preparing 1,2- diamino compounds of formula 45 wherein R', R, R, R, R and R are as above d) acylating the free amino group in position 1 of the 1,2-diamino compound of formula (V) to form an 1. 2 acylated 1,2-diamino compound of formula R1 R2 RNR NH 50 VI 1. 2 and pharmaceutically acceptable addition Salts thereof R1 R2 wherein, R", R, R and R, independently of each other, are H, 55 alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-lower wherein R,R,R,R,R,R, R and Rare as above alkyl, cycloalkyl-lower alkenyl, cycloalkyl-lower and finally alkynyl, heterocyclyl, heterocyclyl-lower alkyl, e) deprotecting the amino group in position 2 of formula heterocyclyl-lower alkenyl, heterocyclyl-lower (VI) to form the 1,2-diamino compound of formula (I). alkynyl, aryl, aryl-lower alkyl, aryl-lower alkenyl, or 60 If desired, the resulting 1,2-diamino compound of formula aryl-lower alkynyl, or (I) can be further transformed into a pharmaceutically R" and R, R and R, R'' and R or R'' and R taken acceptable addition Salt. together with the two carbon atoms to which they are DETAILED DESCRIPTION OF THE bound, are a carbocyclic or heterocyclic ring System, or INVENTION R" and R' or R and R taken together with the carbon 65 The term “alkyl” means a straight chain or branched atom to which they are bound, are a carbocyclic or Saturated alkyl group with 1-20, preferably 1-12, C-atoms, heterocyclic ring System, which can carry one or more Substituents. US 6,437,171 B1 3 4 The term “alkenyl' means a straight chain or branched carboxylate, propyl carboxylate, isopropyl carboxylate and alkenyl group with 2-20, preferably 2-12, C-atoms, which butyl carboxylate. Examples of lower alkanoyl groups are can carry one or more Substituents. acetyl, propionyl and butyryl. The term “alkynyl' means a straight chain or branched In accordance with the present invention, the term "Sub alkynyl group with 2-20, preferably 2-12, C-atoms, which Stituent of an amino group' refers to any Substituents conventionally used to hinder the reactivity of an amino can carry one or more Substituents. group, as described in Green, T., "Protective Groups in The term “cycloalkyl Signifies a Saturated, cyclic hydro Organic Synthesis”, Chapter 7, John Wiley and Sons, Inc., carbon group with 3-12, preferably 5-7, C-atoms, which 1991, 315-385, herein incorporated by reference. Such can carry one or more Substituents. preferred Substituents are acyl, alkyl, alkenyl, alkynyl, aryl The term “aryl” denotes a mono-nuclear or di-nuclear lower alkyl, silyl methyl wherein silyl is trisubstituted with aromatic group which can carry one or more Substituents, lower alkyl, lower alkenyl, lower alkynyl and/or aryl. Such as, for example, phenyl, Substituted phenyl, naphthyl, Advantageously the reactivity of the amino group can also or substituted naphthyl. be hindered by protonation e.g. with Lewis acids, including H. The term "heterocyclyl” means a Saturated or unsaturated 15 monocyclic or bicyclic group with 1 or 2 nitrogen, Sulfur The term “acyl” means alkanoyl, preferably lower and/or oxygen atoms Such as, for example pyranyl, alkanoyl, alkoxy-carbonyl, preferably lower alkoxy dihydropy ranyl, tetrahydropy ranyl, thiopy ranyl, carbonyl, aryloxy-carbonyl or aroyl Such as benzoyl.
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