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Literature DB >> 19761213

Spirodiepoxides: synthesis of epoxomicinoids.

Yue Zhang¹, Joseph R Cusick, Partha Ghosh, Ning Shangguan, Sreenivas Katukojvala, Jennifer Inghrim, Thomas J Emge, Lawrence J Williams.

Abstract

Three closely related analogues of epoxomicin have been synthesized. Allene-derived spirodiepoxides were key intermediates. Spirodiepoxide formation and stereochemical dependence on solvent, oxidant, and allene structure were cataloged. The facial selectivity of the first epoxidation of 1,3-disubstituted and trisubstituted allenes was found to be >20:1 with dimethyldioxirane in chloroform. For stereogenic allenes, the facial selectivity of the second oxidation is dependent primarily on allene structure and secondarily on solvent and oxidant. For the acyclic systems evaluated this ratio was as high as 8:1. A conformational model is advanced to account for these observations.

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Year: 2009 PMID： 19761213 PMCID： PMC3043609 DOI： 10.1021/jo901320f

Source DB: PubMed Journal: J Org Chem ISSN： 0022-3263 Impact factor: 4.354

10 in total

Spirodiepoxides: synthesis of epoxomicinoids.

1. A simple, mild, catalytic, enantioselective addition of terminal acetylenes to aldehydes.

2. The emergence of allenamides in organic synthesis.

3. Synthesis of Unusually Strained Spiro Ring Systems and Their Exploits in Synthesis.

4. Spirodiepoxide reaction with cuprates.

5. Spirodiepoxides: heterocycle synthesis and mechanistic insight.

6. Spirodiepoxides in total synthesis: epoxomicin.

7. A formal synthesis of psymberin.

8. Efficient enantioselective additions of terminal alkynes and aldehydes under operationally convenient conditions.

9. A spirodiepoxide-based strategy to the A-B ring system of pectenotoxin 4.

10. Modeling a macrocyclic bis[spirodiepoxide] strategy to erythronolide A.

1. 1,4-Diazaspiro[2.2]pentanes as a flexible platform for the synthesis of diamine-bearing stereotriads.

2. Total synthesis of (±)-rocaglamide via oxidation-initiated Nazarov cyclization.

3. Synthesis of 1,3-diaminated stereotriads via rearrangement of 1,4-diazaspiro[2.2]pentanes.

4. Spirodiepoxide-based cascades: direct access to diverse motifs.

5. Modular functionalization of allenes to aminated stereotriads.

6. Oxidation-initiated Nazarov cyclization of vinyl alkoxyallenes.

7. Direct entry to erythronolides via a cyclic bis[allene].

8. Spirodiepoxide strategy to the C ring of pectenotoxin 4: synthesis of the C1-C19 sector.

9. Oxidative allene amination for the synthesis of nitrogen-containing heterocycles.

10. Toward an integrated route to the vernonia allenes and related sesquiterpenoids.