Details
| Original language | English |
|---|---|
| Article number | e202302699 |
| Journal | Chemistry - a European journal |
| Volume | 30 |
| Issue number | 3 |
| Early online date | 11 Oct 2023 |
| Publication status | Published - 11 Jan 2024 |
Abstract
Allylic alcohols are a privileged motif in natural product synthesis and new methods that access them in a stereoselective fashion are highly sought after. Toward this goal, we found that chiral acetonide-protected polyketide fragments 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. Various stereodyads and -triads were investigated to determine their substrate induction. The mostly strong inherent stereoinduction was attributed to a combination of steric and electronic effects.
Keywords
- 1,2-metallate rearrangement, allylic alcohols, boron, NHTK, substrate control
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- Chemistry(all)
- Organic Chemistry
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In: Chemistry - a European journal, Vol. 30, No. 3, e202302699, 11.01.2024.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Stereoselective Synthesis of Allylic Alcohols via Substrate Control on Asymmetric Lithiation
AU - Linne, Yannick
AU - Lücke, Daniel
AU - Gerdes, Kjeld
AU - Bajerke, Kevin
AU - Kalesse, Markus
N1 - Funding Information: A generous gift of B2pin2 from Allychem is appreciated. We thank Dr. L. Müggenburg, M. Rettstadt and D. Körtje for detailed NMR analysis and A. Schulz for mass spectra. Open Access funding enabled and organized by Projekt DEAL.
PY - 2024/1/11
Y1 - 2024/1/11
N2 - Allylic alcohols are a privileged motif in natural product synthesis and new methods that access them in a stereoselective fashion are highly sought after. Toward this goal, we found that chiral acetonide-protected polyketide fragments 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. Various stereodyads and -triads were investigated to determine their substrate induction. The mostly strong inherent stereoinduction was attributed to a combination of steric and electronic effects.
AB - Allylic alcohols are a privileged motif in natural product synthesis and new methods that access them in a stereoselective fashion are highly sought after. Toward this goal, we found that chiral acetonide-protected polyketide fragments 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. Various stereodyads and -triads were investigated to determine their substrate induction. The mostly strong inherent stereoinduction was attributed to a combination of steric and electronic effects.
KW - 1,2-metallate rearrangement
KW - allylic alcohols
KW - boron
KW - NHTK
KW - substrate control
UR - http://www.scopus.com/inward/record.url?scp=85177571719&partnerID=8YFLogxK
U2 - 10.1002/chem.202302699
DO - 10.1002/chem.202302699
M3 - Article
AN - SCOPUS:85177571719
VL - 30
JO - Chemistry - a European journal
JF - Chemistry - a European journal
SN - 0947-6539
IS - 3
M1 - e202302699
ER -