The first syntheses of enantiopure 2,2′-biindoline

Chemical Communications

Volumn 46, Issue 48, 2010, Pages 9226-9228

  Wales, Steven M ^a   Willis, Anthony C ^b   Keller, Paul A ^a  

^a UNIVERSITY OF WOLLONGONG   (Australia)

^b AUSTRALIAN NATIONAL UNIVERSITY   (Australia)

Author keywords

[No Author keywords available]

Indexed keywords

2,2' BIAZIRIDINE; 2,2' BIINDOLINE; 2,2' BIOXIRANE; AMINE; COPPER; IODIDE ION; PALLADIUM; SILICA GEL; UNCLASSIFIED DRUG;

ADDITION REACTION; AMINATION; ARTICLE; CATALYSIS; CHEMICAL ANALYSIS; CHEMICAL STRUCTURE; COLUMN CHROMATOGRAPHY; CRYSTALLIZATION; ENANTIOSELECTIVITY; GRIGNARD REACTION; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; HYDROLYSIS; MICROWAVE IRRADIATION; STEREOCHEMISTRY; X RAY ANALYSIS;

EID: 78649653846     PISSN: 13597345     EISSN: None     Source Type: Journal    
DOI: 10.1039/c0cc04045b     Document Type: Article

References (21)

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4. A synthesis of 2,2′-biindoline has been previously reported, presumably as a mixture of all possible isomers, see H. Naarmann, J. Zdenek, H. G. Viehe, M. Beaujean and R. Merenyi, Ger. Offen. 2934131, 1981
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8. 3O by-product remained after this purification process
9. Evidence of a trace quantity of the alternative isomer naphthyridine (S,S)-11 (see Scheme 2) was provided by TLC analysis but no attempt was made to isolate the product in this case
10. 3, THF, RT, 144 h, 76%
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16. 2 in 80% EtOH at reflux and conc. HCl/MeOH (8 1) at reflux were all found to remove the N-Boc substituent but were ineffective in cleavage of the urea
17. The dicarbamate (S,S)-10 was also converted into the diamine (S,S)-7 using typical conditions of TFA at RT in a 66% unoptimised yield
18. The cyclisation reaction was performed using the mixture obtained from the larger scale (incomplete) hydrolysis which contained the diamine (S,S)-7 and the Boc-deprotected imidazolidinone. The yields given are based on the initial quantity of (S,S)-7 present. The latter compound was inert to the cyclisation conditions
19. The enantiomeric purity was determined in the same fashion as that for the product synthesised from bioxirane (R,R)-3
20. Naphthyridine (S,S)-11 is structurally related to the commercially available chiral diamine ligand (4aS,8aS)-decahydro-1,5-naphthyridine, which is used in copper catalysed enantioselective aryl homo-coupling reactions. Therefore, it is of interest to us to investigate a method to reverse the regioselectivity of the cyclisation in order to obtain larger quantities of naphthyridine (S,S)-11 for its testing as a new chiral ligand
21. The corresponding (R,R)-biindoline would be accessible in the same fashion from the bioxirane and biaziridine precursors derived from l-tartaric acid