Total Syntheses of HMP-Y1, Hibarimicinone, and HMP-P1

DSpace/Manakin Repository

Total Syntheses of HMP-Y1, Hibarimicinone, and HMP-P1

Citable link to this page

. . . . . .

Title: Total Syntheses of HMP-Y1, Hibarimicinone, and HMP-P1
Author: Liau, Brian Bor-Jen; Milgram, Benjamin Charles; Shair, Matthew David

Note: Order does not necessarily reflect citation order of authors.

Citation: Liau, Brian B., Benjamin C. Milgram, Matthew D. Shair. 2012. Total syntheses of HMP-Y1, hibarimicinone, and HMP-P1. Journal of the American Chemical Society 134(40): 16765–16772.
Full Text & Related Files:
Abstract: Total syntheses of HMP-Y1, atrop-HMP-Y1, hibarimicinone, atrop-hibarimicinone, and HMP-P1 are described using a two-directional synthesis strategy. A novel benzyl fluoride Michael–Claisen reaction sequence was developed to construct the complete carbon skeleton of HMP-Y1 and atrop-HMP-Y1 via a symmetrical, two-directional, double annulation. Through efforts to convert HMP-Y1 derivatives to hibarimicinone and HMP-P1, a biomimetic mono-oxidation to desymmetrize protected HMP-Y1 was realized. A two-directional unsymmetrical double annulation and biomimetic etherification were developed to construct the polycyclic and highly-oxidized skeleton of hibarimicinone, atrop-hibarimicinone, and HMP-P1. The use of a racemic biaryl precursor allowed for the synthesis of both hibarimicinone atropisomers and provides the first confirmation of the structure of atrop-hibarimicinone. Additionally, this work documents the first reported full characterization of atrop-hibarimicinone, HMP-Y1, atrop-HMP-Y1, and HMP-P1. Lastly, a pH-dependent rotational barrier about the C2–C2' bond of hibarimicinone was discovered, which provides valuable information necessary to achieve syntheses of the glycosylated congeners of hibarimicinone.
Published Version: doi:10.1021/ja307207q
Terms of Use: This article is made available under the terms and conditions applicable to Open Access Policy Articles, as set forth at http://nrs.harvard.edu/urn-3:HUL.InstRepos:dash.current.terms-of-use#OAP
Citable link to this page: http://nrs.harvard.edu/urn-3:HUL.InstRepos:9639969

Show full Dublin Core record

This item appears in the following Collection(s)

  • FAS Scholarly Articles [6464]
    Peer reviewed scholarly articles from the Faculty of Arts and Sciences of Harvard University
 
 

Search DASH


Advanced Search
 
 

Submitters