Details
| Original language | English |
|---|---|
| Pages (from-to) | 1695-1710 |
| Number of pages | 16 |
| Journal | JACS Au |
| Volume | 3 |
| Issue number | 6 |
| Early online date | 22 May 2023 |
| Publication status | Published - 26 Jun 2023 |
Abstract
Stereotriads bearing allylic alcohols are privileged structures in natural products, and new methods accessing these in a stereoselective fashion are highly sought after. Toward this goal, we found that the use of chiral polyketide fragments allows for performing the Hoppe-Matteson-Aggarwal rearrangement in the absence of sparteine with high yields and diastereoselectivities, rendering this protocol a highly valuable alternative to the Nozaki-Hiyama-Takai-Kishi reaction. The switch of directing groups in most cases resulted in the reversed stereochemical outcome, which could be explained by conformational analysis on density functional theory level and a Felkin-like model.
Keywords
- chiral anions, conformational analysis, Hoppe−Matteson−Aggarwal rearrangement, Nozaki−Hiyama−Takai−Kishi reaction, polyketides
ASJC Scopus subject areas
- Chemistry(all)
- Analytical Chemistry
- Chemistry(all)
- Chemistry (miscellaneous)
- Chemistry(all)
- Physical and Theoretical Chemistry
- Chemistry(all)
- Organic Chemistry
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In: JACS Au, Vol. 3, No. 6, 26.06.2023, p. 1695-1710.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Sparteine-Free, Highly Stereoselective Construction of Complex Allylic Alcohols Using 1,2-Metallate Rearrangements
AU - Linne, Yannick
AU - Birkner, Maike
AU - Flormann, Jan
AU - Lücke, Daniel
AU - Becker, Jörg August
AU - Kalesse, Markus
N1 - Funding Information: This work was supported by the Deutsche Forschungsgemeinschaft (DFG) KA 913/24-1.
PY - 2023/6/26
Y1 - 2023/6/26
N2 - Stereotriads bearing allylic alcohols are privileged structures in natural products, and new methods accessing these in a stereoselective fashion are highly sought after. Toward this goal, we found that the use of chiral polyketide fragments allows for performing the Hoppe-Matteson-Aggarwal rearrangement in the absence of sparteine with high yields and diastereoselectivities, rendering this protocol a highly valuable alternative to the Nozaki-Hiyama-Takai-Kishi reaction. The switch of directing groups in most cases resulted in the reversed stereochemical outcome, which could be explained by conformational analysis on density functional theory level and a Felkin-like model.
AB - Stereotriads bearing allylic alcohols are privileged structures in natural products, and new methods accessing these in a stereoselective fashion are highly sought after. Toward this goal, we found that the use of chiral polyketide fragments allows for performing the Hoppe-Matteson-Aggarwal rearrangement in the absence of sparteine with high yields and diastereoselectivities, rendering this protocol a highly valuable alternative to the Nozaki-Hiyama-Takai-Kishi reaction. The switch of directing groups in most cases resulted in the reversed stereochemical outcome, which could be explained by conformational analysis on density functional theory level and a Felkin-like model.
KW - chiral anions
KW - conformational analysis
KW - Hoppe−Matteson−Aggarwal rearrangement
KW - Nozaki−Hiyama−Takai−Kishi reaction
KW - polyketides
UR - http://www.scopus.com/inward/record.url?scp=85162855345&partnerID=8YFLogxK
U2 - 10.1021/jacsau.3c00114
DO - 10.1021/jacsau.3c00114
M3 - Article
AN - SCOPUS:85162855345
VL - 3
SP - 1695
EP - 1710
JO - JACS Au
JF - JACS Au
IS - 6
ER -