Stereospecific construction of contiguous quaternary and tertiary stereocenters by rearrangement from indoline-2-methanol to 2,2,3-trisubstituted tetrahydroquinoline: Application to an efficient total synthesis of natural virantmycin

Angewandte Chemie - International Edition

Volumn 42, Issue 22, 2003, Pages 2540-2543

  Ori, Mayuko ^a   Toda, Narihiro ^a   Takami, Kazuko ^a   Tago, Keiko ^a   Kogen, Hiroshi ^a  

^a DAIICHI SANKYO CO   (Japan)

Author keywords

Alkaloids; Natural products; Rearrangement; Total synthesis

Indexed keywords

METHANOL; SUBSTITUTION REACTIONS; SYNTHESIS (CHEMICAL);

STEREOSPECIFIC CONSTRUCTION;

STEREOCHEMISTRY;

INDOLE DERIVATIVE; INDOLINE 2 METHANOL; METHANOL DERIVATIVE; QUINOLINE DERIVATIVE; UNCLASSIFIED DRUG; VIRANTMYCIN;

ARTICLE; DRUG STRUCTURE; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOSPECIFICITY; STRUCTURE ANALYSIS; X RAY ANALYSIS;

ANTIVIRAL AGENTS; INDOLES; METHANOL; MODELS, MOLECULAR; MOLECULAR STRUCTURE; QUINOLINES; STEREOISOMERISM;

EID: 0038339570     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200351069     Document Type: Article

References (28)

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14. -1.
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17. CCDC 202237 (7) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44)1223-336-033; or deposit@ccdc.cam.ac.uk).
18. There is no direct evidence for the formation of an aziridine: intermediate such as 4. A stepwise sequence may be possible (1. formation of tertiary chloride; 2. intermolecular cyclization to an aziridine: 3. ring opening by the attack of chloride anion). However, we could not obtain the tertiary chloride by treatment of 1a with various chlorinating agents. Also, treatment of 1a under Mitsunobu conditions gave no aziridine compound (starting material waas recovered). For the ring-opening reaction of an aziridine, such as 4, with chloride anions to provide tetrahydroquinoline 2, see ref. [10].
19. All the other products were highly polar materials which are not isolated.
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27. When we used triphenylphosphane in the reaction, an undesired deiodinated product and an indole derivative (dehydration followed by isomerization) were obtained. However, using tri-n-butylphosphane instead of triphenylphosphane presented these side reactions.
28. Initially, the optical rotation of (-)-virantmycin was reported as -0.05 in ref. [3]. Later, the optical rotation of (-)-virantmycin was reexamined and reported as -11.1 by Shirahama and co-workers.[16]