Angucyclinone antibiotics: total syntheses of ym-181741, (+)-ochromycinone, (+)-rubiginone b-2, (-)-tetrangomycin, and mm-47755
DSpace at IIT Bombay
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Title |
Angucyclinone antibiotics: total syntheses of ym-181741, (+)-ochromycinone, (+)-rubiginone b-2, (-)-tetrangomycin, and mm-47755
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Creator |
KALIAPPAN, KP
RAVIKUMAR, V |
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Subject |
ring-closing metathesis
enantioselective total-synthesis diels-alder reaction medium-sized rings helicobacter-pylori olefin metathesis enyne metathesis organic-synthesis urdamycinone-b racemic vinylcyclohexenes |
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Description |
A concise and highly enantioselective route has been developed for the synthesis of angucyclinone-type natural products. Utilizing this strategy, total syntheses of five natural products YM-181741, (+)-ochromycinone, (+)-rubiginone B-2, (-)-tetrangomycin, and MM-47755 have been accomplished in 22%, 23%, 19%, 18%, and 12% overall yields, respectively. Our approach for the synthesis of these natural products having the benz[a]anthraquinone skeleton is based on a sequential intramolecular enyne metathesis, intermolecular Diels-Alder reaction (DAR), and aromatization. The intramolecular enyne metathesis reaction was employed for the synthesis of enantiopure 1,3-dienes in excellent yields. Furthermore, the synthesis of YM-181741 as well as structurally similar angucyclinones such as (+)-ochromycinone and (+)-rubiginone B-2 was achieved via asymmetric enolate alkylation of an oxazolidinone in excellent de. The related angucyclinones (-)-tetrangomycin and MM-47755, bearing a labile tertiary alcohol, were synthesized via Sharpless asymmetric epoxidation of a known allylic alcohol followed by opening the epoxide with Red-Al. The introduction of oxygen functionality at C-1 in all these natural products was accomplished by photooxygenation under a positive pressure of oxygen.
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Publisher |
AMER CHEMICAL SOC
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Date |
2011-10-15T06:26:22Z
2011-12-15T09:16:20Z 2011-10-15T06:26:22Z 2011-12-15T09:16:20Z 2007 |
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Type |
Review
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Identifier |
JOURNAL OF ORGANIC CHEMISTRY,72(16)6116-6126
0022-3263 http://dx.doi.org/10.1021/jo070709p http://dspace.library.iitb.ac.in/xmlui/handle/10054/13936 http://hdl.handle.net/100/3115 |
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Language |
en
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