Asymmetric Syntheses of 2-Substituted and 2,5-Disubstituted Pyrrolidines from (3S,5R,7aR)-5-(Benzotriazol-1-yl)-3-phenyl[2,1-b]oxazolopyrrolidine

Katritzky, Alan R.; Cui, Xilin; Yang, Baozhen; Steel, Peter J.

doi:10.1021/jo9821426

Cited by 83 publications

(50 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…8) Shono 9) and co-workers reported the phosphonylation of Nprotected 2-methoxyamines using trialkyl phosphites in the presence of Lewis acids. Similar transformation of 2-benzotriazolylpyrrolidine derivatives into pyrrolidine-2-phosphonic acid esters was reported by Katritzky 10) and co-workers. We wish to report herein the convenient conversion of cyclic aamino acids to cyclic a-aminophosphonic acids through the corresponding N-protected 2-hydroxyamines, with which easy generation of acyliminium ions in the presence of Lewis acids would be expected.…”

supporting

confidence: 83%

Chemical Conversion of Cyclic .ALPHA.-Amino Acids to Cyclic .ALPHA.-Aminophosphonic Acids.

Kaname¹,

Mashige

Yoshifuji

2001

Chem. Pharm. Bull.

View full text Add to dashboard Cite

a-Aminophosphonic acids are believed to be phosphorus analogs of naturally occurring a-amino acids and have found applications as potent active compounds with a wide range of biological activities as antibiotics, 1) enzyme inhibitors,2) pharmacological agents, 2b,3) antiviral agents, 4) and herbicides.5) Their negligible mammalian toxicity, and the fact that they bear a very close chemical resemblance to their amino carboxylic counterparts, make them remarkably important structural units of phosphonopeptides and peptidomimetics.6) During the last two decades, considerable efforts toward the synthesis of a-aminophosphonic acids have been made. 7) However, a simple and general synthetic method for cyclic amino-type of compounds, such as phosphonic acid analogs of 2-pyrrolidinecarboxylic acid (proline) and 2-piperidinecarboxylic acid, is not relatively known, and most of the reported methods are about acyclic compounds. The cyclic analogues can be viewed as useful tools for the elucidation of conformational requirements of a receptor, since the conformation is easily fixed. Many synthetic routes to a-aminophosphonic acids and their derivatives include a key step of nucleophilic phosphonylation to either performed or in situ generated imines (Schiff bases) or iminium ions. 8)Shono 9) and co-workers reported the phosphonylation of Nprotected 2-methoxyamines using trialkyl phosphites in the presence of Lewis acids. Similar transformation of 2-benzotriazolylpyrrolidine derivatives into pyrrolidine-2-phosphonic acid esters was reported by Katritzky 10) and co-workers. We wish to report herein the convenient conversion of cyclic aamino acids to cyclic a-aminophosphonic acids through the corresponding N-protected 2-hydroxyamines, with which easy generation of acyliminium ions in the presence of Lewis acids would be expected. To our knowledge, only a few studies concerning the chemical conversion of naturally occurring cyclic a-amino acid (proline or proline-containing dipeptide) into the corresponding phosphonic acid analogues have been published, 11,12) and these are not systematic or detailed studies. In this paper, we describe a systematic study on a simple route to a series of phosphonic acid analogues from proline and 2-piperidinecarboxylic acid, as illustrated in Chart 1.Initially, we examined the transformation of commercially available cyclic a-amino acids (1, 2) into the key intermediates of cyclic N-protected 2-hydroxyamines (5, 6). Displacement of the carboxylic acid moiety by hydroxy group or its equivalents such as acetoxy group had been realized by using two methods of oxidative decarboxylation: lead tetraacetate [Pb(OAc) 4 ] oxidation 13) of carboxylic acids and m-chloroperbenzoic acid (m-CPBA) oxidation 14) of active esters. We applied these methods to N-protected amino acids (3a-e, 4a-c) and their active esters (3f, g), as summarized in Table1. L-Proline derivatives (3a-e) having various N-protecting groups were oxidized with Pb(OAc) 4 to the desired 2-hydroxy compounds (5a-e) in good yields. N-Benzoyl (B...

show abstract

supporting

confidence: 83%

Chemical Conversion of Cyclic .ALPHA.-Amino Acids to Cyclic .ALPHA.-Aminophosphonic Acids.

Kaname¹,

Mashige

Yoshifuji

2001

Chem. Pharm. Bull.

View full text Add to dashboard Cite

show abstract

“…Data are in agreement with previously reported results. 9 Catalyst I was prepared by a modification of II. Diisopropyl (2R)-tetrahydro-1H-pyrrol-2-ylphosphonate I: A solution of starting material (1 mmol) in ethanol (60 ml) with 10% Pd(OH) 2 /C (50 mg) was charged with hydrogen at a pressure of 40 psi at rt for 24 h. After filtration of the catalyst, the filtrate was treated with HCl in EtOAc (2 M) and stirred at rt for 30 min.…”

Section: Methodsmentioning

confidence: 99%

“…Pyrrolidine-pyridine, 5 pyrrolidine-thiourea, derivatives, 6 and fluorouspyrrolidine sulfonamide 7 and chiral diamine, 8 have also served as powerful asymmetric catalysts for such Michael additions. Herein, we wish to add a new example to these entries by revealing for the first time that readily available cyclic a-aminophosphonates [9][10][11] can also serve as efficient catalysts for Michael addition.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

α‐Aminophosphonates as novel organocatalysts for asymmetric Michael addition of carbonyl compounds to nitroolefins

et al. 2008

View full text Add to dashboard Cite

show abstract

“…[58][59][60][61][62] Hydrogenolysis of 82, followed by acidic hydrolysis of the phosphonate moiety with 6 M HCl and subsequent treatment with propylene oxide led to (S)-phosphopyrrolidine 25 (Scheme 30). …”

Section: Scheme 30mentioning

confidence: 99%

Synthetic methods of cyclic α-aminophosphonic acids and their esters

Ali¹

2013

Arkivoc

View full text Add to dashboard Cite

show abstract

Asymmetric Syntheses of 2-Substituted and 2,5-Disubstituted Pyrrolidines from (3S,5R,7aR)-5-(Benzotriazol-1-yl)-3-phenyl[2,1-b]oxazolopyrrolidine

Cited by 83 publications

References 35 publications

Chemical Conversion of Cyclic .ALPHA.-Amino Acids to Cyclic .ALPHA.-Aminophosphonic Acids.

Chemical Conversion of Cyclic .ALPHA.-Amino Acids to Cyclic .ALPHA.-Aminophosphonic Acids.

α‐Aminophosphonates as novel organocatalysts for asymmetric Michael addition of carbonyl compounds to nitroolefins

Synthetic methods of cyclic α-aminophosphonic acids and their esters

Contact Info

Product

Resources

About