Synthesis of all four enantiomers of 1-aminoindane-2-carboxylic acid, a new cispentacin benzologue

Fülöp, Ferenc; Palkó, Márta; Kámán, Judit; Lázár, László; Sillanpää, Reijo

doi:10.1016/s0957-4166(00)00375-x

Cited by 30 publications

(16 citation statements)

References 22 publications

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“…A kinetic resolution employing Lipase B was carried out to yield a separable mixture of β -amino acid (−)- 9 and β -lactam (+)- 8 , both in 99 % e.e. 25–27 The enantiomeric excess was determined by Supercritical Fluid Chromatography (SFC), as described in the Supporting Information. The β -amino acid (−)- 9 was next converted to the cis indanol (+)- 11 in two steps.…”

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confidence: 99%

Structure-Based Design and Synthesis of an HIV-1 Entry Inhibitor Exploiting X-ray and Thermodynamic Characterization

LaLonde

Le-Khac

Jones

et al. 2013

ACS Med. Chem. Lett.

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The design, synthesis, thermodynamic and crystallographic characterization of a potent, broad spectrum, second-generation HIV-1 entry inhibitor that engages conserved carbonyl hydrogen bonds within gp120 has been achieved. The optimized antagonist exhibits a sub-micromolar binding affinity (110 nM) and inhibits viral entry of clade B and C viruses (IC50 geometric mean titer of 1.7 and 14.0 μM, respectively), without promoting CD4-independent viral entry. thermodynamic signatures indicate a binding preference for the (R,R)-over the (S,S)-enantiomer. The crystal structure of the small molecule-gp120 complex reveals the displacement of crystallographic water and the formation of a hydrogen bond with a backbone carbonyl of the bridging sheet. Thus, structure-based design and synthesis targeting the highly conserved and structurally characterized CD4:gp120 interface is an effective tactic to enhance the neutralization potency of small molecule HIV-1 entry inhibitors.

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confidence: 99%

Structure-Based Design and Synthesis of an HIV-1 Entry Inhibitor Exploiting X-ray and Thermodynamic Characterization

LaLonde

Le-Khac

Jones

et al. 2013

ACS Med. Chem. Lett.

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“…The absolute configuration in the case of 16 was proved by comparing the [a] value with the literature data [13] ( Table 5), whereas for its six-and seven-membered homologues the analyzed chromatograms indicated the same enantioselectivity preference for Lipolase.…”

Section: Resultsmentioning

confidence: 97%

“…[13][14][15] In order to synthesize the seven-membered b-lactam (AE )-6, benzosuberene (3), the substrate for CSI addition, was first prepared from 1-benzosuberone by means of NaBH 4 reduction and subsequent H 2 O elimina- [16] All the reactions took place regio-and stereoselectively: not even traces of other regio-or stereoisomers were detected. As the racemic six-and seven-membered b-amino acids are new compounds, the transformations of (AE )-5 and (AE )-6 by ring opening with 18 % HCl were also performed, resulting in b-amino acid hydrochlorides (AE )-8 and (AE )-9, respectively (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

“…[13] www.chemeurj.org Data for 13: The 1 H NMR (400 MHz, CDCl 3 , 258C, TMS) data are similar to those for (AE )-4; elemental analysis calcd (%) for C 10 H 9 NO: C 75.45,H 5.70,N 8.80;found: C 75.42,H 5.59,N 8.77 10 H 11 NO 2 : C 67.78,H 6.26,N 7.90;found: C 67.47,H 6.25,N 7.98 H 5.66, N 5.56; found: C 55.88, H 5.40, N 5.58.…”

Section: Gram-scale Resolution Of Racemic (Ae )-4 (Ae )-5 and (Ae )-6mentioning

confidence: 97%

“…Synthesis of (AE )-4: By using the literature procedure [13] and indene (11.62 g, 0.10 mol), (AE )-4 was obtained (11.44 g,72 %;recrystallized from AcOEt and MeOH,. 1, 54.9, 59.2, 125.8, 127.0, 127.8, 129.8, 141.2, 144.5, 172.0 ppm; elemental analysis calcd (%) for C 10 H 9 NO: C 75.…”

Section: 0]-nonan-9-one ((Ae )-4 (Ae )-5 and (Ae )-6)mentioning

confidence: 99%

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An Efficient Enzymatic Synthesis of Benzocispentacin and Its New Six‐ and Seven‐Membered Homologues

Forró¹,

Fülöp²

2006

Chemistry A European J

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A very efficient enzymatic method was developed for the synthesis of new enantiomeric benzocispentacin and its six- and seven-membered homologues through the Lipolase (lipase B from Candida antarctica) catalyzed enantioselective (E > 200) ring opening of 3,4-benzo-6-azabicyclo[3.2.0]heptan-7-one, 4,5-benzo-7-azabicyclo[4.2.0]octan-8-one, and 5,6-benzo-8-azabicyclo[5.2.0]nonan-9-one with H2O in iPr2O at 60 degrees C. The (1R,2R)-beta-amino acids (ee > or = 96%, yields > or = 40%) and (1S,6S)-, (1S,7S)-, and (1S,8S)-beta-lactams (ee > 99%, yields > or = 44%) produced could be easily separated. The ring opening of racemic and enantiomeric beta-lactams with 18% HCl afforded the corresponding beta-amino acid hydrochlorides.

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Synthesis of Carbocyclic β‐Amino Acids

Kiss

Forró

Fülöp

2009

Amino Acids, Peptides and Proteins in Organic Chemistry

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j367 acids was reviewed by our group in 2001 [1]; the present chapter highlights the chemistry of these compounds published since 2000, with the aim of offering the reader an insight into the most recent developments in this field. Synthesis of Carbocyclic b-Amino AcidsOwing to their significance, a number of methods have been developed for the synthesis of these conformationally restricted molecules in racemic and enantiomerically pure form. The largest groups of carbocyclic b-amino acids and the most intensively investigated are the fiveand six-membered derivatives. One main method of preparation consists of the amidation of 1,2-dicarboxylic anhydrides 4, followed by Hoffmann rearrangement of the resulting amide 5 to amino acid 7. The same starting material, the meso anhydride 4, undergoes partial hydrolysis, followed by the Curtius rearrangement, to give 2-aminocyclohexanecarboxylic acid 7 (Scheme 8.1) ([1] and references cited therein).A widely used method for the synthesis of carbocyclic b-amino acids is the transformation of cycloalkenes via the corresponding bicyclic b-lactams. The 1,2dipolar cycloaddition of chlorosulfonyl isocyanate (CSI) to cycloalkenes 8 led regioselectively to the cycloalkane-fused b-lactams 10, whose acidic hydrolysis resulted in lactam ring opening and formation of the carbocyclic b-amino acid hydrochlorides 11 (Scheme 8.2) ([1] and references cited therein). O O O NH 4 OH COOH CONH 2 1. ROH 2. HO 3. H COOR COOH Curtius degradation COOH NH 2 Hoffmann degradation NaOH, Br 2 1. SOCl 2 2. NaN 3 Dowex 4 5 6 7 Scheme 8.1 Synthesis of carbocyclic b-amino acids by Curtius and Hoffmann rearrangements. CSI NSO 2 Cl O H 2 O NH O HCl, RT COOH NH 2 HCl 8 9 10 11 Scheme 8.2 Synthesis of carbocyclic b-amino acids from b-lactams. 368j 8 Synthesis of Carbocyclic b-Amino Acids 15 16 18 17 16:17:18 = 95.5:1.7:2.8 KOtBu, tBuOH ∆, 3hScheme 8.4 Synthesis of 3-methylcispentacin derivatives by conjugate addition. Synthesis of Carbocyclic b-Amino Acids j369To prepare 3-methyltranspentacin, aminocarboxylate 17 was first obtained in a larger quantity from diastereoisomer 16 by epimerization on treatment with KOtBu in tBuOH; this afforded 17 in quantitative yield and a diastereomeric excess of 99%. N-Deprotection of 17, followed by ester hydrolysis, gave the desired 3-methyltranspentacin in 97% e.e. [9].By using this conjugate addition methodology, Davies et al. also prepared 5-substituted derivatives of cispentacin. The addition of lithium amide (S)-13 to 5-isopropyl-, 5-phenyl-, and 5-tert-butylcyclopentenecarboxylates proceeded with a high degree of selectivity, the major derivatives formed having the amine anti to the 5-alkyl group. N-Deprotection by hydrogenolysis, subsequent acid hydrolysis of the ester, and ion-exchange chromatography furnished 5-substituted cispentacin derivatives in 98% e.e. [10].The asymmetric synthesis of a series of functionalized derivatives was achieved by using amine conjugate addition processes. Four stereoisomers of 2-amino-5carboxymethylcyclopentanecarboxylate were prepared ...

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Synthesis of all four enantiomers of 1-aminoindane-2-carboxylic acid, a new cispentacin benzologue

Cited by 30 publications

References 22 publications

Structure-Based Design and Synthesis of an HIV-1 Entry Inhibitor Exploiting X-ray and Thermodynamic Characterization

Structure-Based Design and Synthesis of an HIV-1 Entry Inhibitor Exploiting X-ray and Thermodynamic Characterization

An Efficient Enzymatic Synthesis of Benzocispentacin and Its New Six‐ and Seven‐Membered Homologues

Synthesis of Carbocyclic β‐Amino Acids

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