Abstract
The presence of a bromide substituent, instead of a hydrogen or methyl group, on a carbon-carbon double bond, protects the alkene from addition reactions when exposed to trifluoroacetic acid. This concept is used to circumvent concomitant loss of unsaturation in a late-stage acid-catalysed 6,8- to 2,8-dioxabicyclo[3.2.1]octane rearrangement towards (-)-6,7-dideoxysqualestatin H5. The inertness of the alkenyl bromide functionality is demonstrated through several synthetic transformations in the assembly of the rearrangement substrate. Completion of the natural product synthesis is facilitated by post-rearrangement removal of the bromide substituent through stereoselective C-C cross-coupling in the presence of ester and hydroxyl functionalities.
| Original language | English |
|---|---|
| Pages (from-to) | 5354-5356 |
| Number of pages | 3 |
| Journal | Chemical Communications |
| Volume | 54 |
| Issue number | 42 |
| DOIs | |
| Publication status | Published - Jan 1 2018 |
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ASJC Scopus subject areas
- Catalysis
- Electronic, Optical and Magnetic Materials
- Ceramics and Composites
- Chemistry(all)
- Surfaces, Coatings and Films
- Metals and Alloys
- Materials Chemistry
Cite this
Alkene protection against acid using a bromide substituent : Application in a total synthesis of (-)-6,7-dideoxysqualestatin H5. / Almohseni, Hasanain A.A.; Al Mamari, Hamad; Valade, Anne; Sintim, Herman O.; Hodgson, David M.
In: Chemical Communications, Vol. 54, No. 42, 01.01.2018, p. 5354-5356.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Alkene protection against acid using a bromide substituent
T2 - Application in a total synthesis of (-)-6,7-dideoxysqualestatin H5
AU - Almohseni, Hasanain A.A.
AU - Al Mamari, Hamad
AU - Valade, Anne
AU - Sintim, Herman O.
AU - Hodgson, David M.
PY - 2018/1/1
Y1 - 2018/1/1
N2 - The presence of a bromide substituent, instead of a hydrogen or methyl group, on a carbon-carbon double bond, protects the alkene from addition reactions when exposed to trifluoroacetic acid. This concept is used to circumvent concomitant loss of unsaturation in a late-stage acid-catalysed 6,8- to 2,8-dioxabicyclo[3.2.1]octane rearrangement towards (-)-6,7-dideoxysqualestatin H5. The inertness of the alkenyl bromide functionality is demonstrated through several synthetic transformations in the assembly of the rearrangement substrate. Completion of the natural product synthesis is facilitated by post-rearrangement removal of the bromide substituent through stereoselective C-C cross-coupling in the presence of ester and hydroxyl functionalities.
AB - The presence of a bromide substituent, instead of a hydrogen or methyl group, on a carbon-carbon double bond, protects the alkene from addition reactions when exposed to trifluoroacetic acid. This concept is used to circumvent concomitant loss of unsaturation in a late-stage acid-catalysed 6,8- to 2,8-dioxabicyclo[3.2.1]octane rearrangement towards (-)-6,7-dideoxysqualestatin H5. The inertness of the alkenyl bromide functionality is demonstrated through several synthetic transformations in the assembly of the rearrangement substrate. Completion of the natural product synthesis is facilitated by post-rearrangement removal of the bromide substituent through stereoselective C-C cross-coupling in the presence of ester and hydroxyl functionalities.
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UR - http://www.scopus.com/inward/citedby.url?scp=85047493501&partnerID=8YFLogxK
U2 - 10.1039/c8cc02690d
DO - 10.1039/c8cc02690d
M3 - Article
VL - 54
SP - 5354
EP - 5356
JO - Chemical Communications
JF - Chemical Communications
SN - 1359-7345
IS - 42
ER -