Biosynthesis of blasticidin S : mechanistic and stereochemical investigations Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/b2773z07d

Descriptions

Attribute NameValues
Creator
Abstract or Summary
  • Feeding of [3-¹³C, 2-¹⁵N]arginine, 38a, unequivocally established that the β- arginine moiety of blasticidin S, 1, was formed from α-arginine by an intramolecular migration of the α-amino group to the β- position. Further feedings using chirally deuteriated arginines 38e and 38f revealed that the aminomutase process occurred with inversion of configuration at C-3 of arginine and the 3-pro-R hydrogen was involved in the migration from C-3 to C-2. Efforts to assign the absolute stereochemistry of alcohols 45a and 45b, intermediates in the synthesis of 38e and 38f, led to the discovery that the Gerlach- Zagalak analysis of their corresponding (-)-camphanates had yielded results contrary to the well established empirical rule, the first time this had been observed. Synthesis and feeding of labeled β- arginine 23a was carried out and the result supported the proposed intermediacy of β-arginine in the biosynthetic pathway to 1. Initial attempts to detect the putative arginine-2,3-aminomutase activity in cell-free extracts of S. griseochromogenes have not been successful so far. Feeding [2,3,4,6,6- ²H₅] -D- glucose resulted in blasticidin S 11 in which deuterium from H-2 and H-3 had been retained at H-6 and H-7, respectively. This interesting result led to the proposal of a novel mechanism for the introduction of a double bond in the hexeneuronic acid moiety of 1, and ruled out other mechanisms involving a β-eliminative dehydration process.
Resource Type
Date Available
Date Copyright
Date Issued
Degree Level
Degree Name
Degree Field
Degree Grantor
Commencement Year
Advisor
Academic Affiliation
Non-Academic Affiliation
Subject
Rights Statement
Peer Reviewed
Language
Digitization Specifications
  • File scanned at 300 ppi (Monochrome) using Capture Perfect 3.0.82 on a Canon DR-9080C in PDF format. CVista PdfCompressor 4.0 was used for pdf compression and textual OCR.
Replaces
Additional Information
  • description.provenance : Approved for entry into archive by Patricia Black(patricia.black@oregonstate.edu) on 2013-05-29T16:00:17Z (GMT) No. of bitstreams: 1 PrabhakaranPC1989.pdf: 1614623 bytes, checksum: 303ec55aaa5507c47c9716e185addcf8 (MD5)
  • description.provenance : Made available in DSpace on 2013-07-02T14:46:09Z (GMT). No. of bitstreams: 1 PrabhakaranPC1989.pdf: 1614623 bytes, checksum: 303ec55aaa5507c47c9716e185addcf8 (MD5) Previous issue date: 1988-07-08
  • description.provenance : Submitted by Kim Stowell (ksscannerosu@gmail.com) on 2013-05-17T00:45:14Z No. of bitstreams: 1 PrabhakaranPC1989.pdf: 1614623 bytes, checksum: 303ec55aaa5507c47c9716e185addcf8 (MD5)
  • description.provenance : Approved for entry into archive by Deborah Campbell(deborah.campbell@oregonstate.edu) on 2013-07-02T14:46:09Z (GMT) No. of bitstreams: 1 PrabhakaranPC1989.pdf: 1614623 bytes, checksum: 303ec55aaa5507c47c9716e185addcf8 (MD5)

Relationships

In Administrative Set:
Last modified: 08/04/2017

Downloadable Content

Download PDF
Citations:

EndNote | Zotero | Mendeley

Items