Alkene protection against acid using a bromide substituent: Application in a total synthesis of (-)-6,7-dideoxysqualestatin H5

Hasanain A.A. Almohseni; Hamad H. Al Mamari; Anne Valade; Herman O. Sintim; David M. Hodgson

doi:10.1039/c8cc02690d

Alkene protection against acid using a bromide substituent: Application in a total synthesis of (-)-6,7-dideoxysqualestatin H5

Hasanain A.A. Almohseni, Hamad H. Al Mamari, Anne Valade, Herman O. Sintim, David M. Hodgson^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

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	https://doi.org/10.1039/c8cc02690d
Publication status	Published - 2018
Externally published	Yes

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Ceramics and Composites
Metals and Alloys
Materials Chemistry
Surfaces, Coatings and Films
General Chemistry
Catalysis

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10.1039/c8cc02690d

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title = "Alkene protection against acid using a bromide substituent: Application in a total synthesis of (-)-6,7-dideoxysqualestatin H5",

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.",

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doi = "10.1039/c8cc02690d",

language = "English",

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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 H.

AU - Valade, Anne

AU - Sintim, Herman O.

AU - Hodgson, David M.

PY - 2018

Y1 - 2018

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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Alkene protection against acid using a bromide substituent: Application in a total synthesis of (-)-6,7-dideoxysqualestatin H5

Abstract

ASJC Scopus subject areas

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