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Selective bromochlorination of a homoallylic alcohol for the total synthesis of ( − )-anverene

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ABSTRACT

The scope of a recently reported method for the catalytic enantioselective bromochlorination of allylic alcohols is expanded to include a specific homoallylic alcohol. Critical factors for optimization of this reaction are highlighted. The utility of the product bromochloride is demonstrated by the first total synthesis of an antibacterial polyhalogenated monoterpene, (−)-anverene.

No MeSH data available.


Selective bromochlorination and possible disconnections for anverene (1).
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C1: Selective bromochlorination and possible disconnections for anverene (1).

Mentions: Several years ago our laboratory developed the first catalytic enantioselective dibromination of cinnamyl alcohols [6]. Unfortunately, this method suffered from the requirement for electronically biased substrates, and the catalyst system was not applicable to other dihalogenation reactions. In 2015, we disclosed a much-improved catalytic enantioselective bromochlorination protocol that is able to override inherent substrate regioselectivity [7]. This development vastly expanded the substrate scope to include a larger subset of alkyl-substituted allylic alcohols (Scheme 1, top); the relative and absolute stereochemical configurations of all resulting bromochlorides have been assigned and are shown for the (R,S) Schiff base ligand [7–9]. Furthermore, the reaction conditions could now be modulated to affect both catalytic enantioselective dichlorination and dibromination of allylic alcohols [9]. The utility of this method has been demonstrated by highly selective total syntheses of several important polyhalogenated natural product targets including (+)-halomon [8] and (−)-danicalipin A [9].


Selective bromochlorination of a homoallylic alcohol for the total synthesis of ( − )-anverene
Selective bromochlorination and possible disconnections for anverene (1).
© Copyright Policy - Beilstein
Related In: Results  -  Collection

License 1 - License 2
Show All Figures
getmorefigures.php?uid=PMC4979643&req=5

C1: Selective bromochlorination and possible disconnections for anverene (1).
Mentions: Several years ago our laboratory developed the first catalytic enantioselective dibromination of cinnamyl alcohols [6]. Unfortunately, this method suffered from the requirement for electronically biased substrates, and the catalyst system was not applicable to other dihalogenation reactions. In 2015, we disclosed a much-improved catalytic enantioselective bromochlorination protocol that is able to override inherent substrate regioselectivity [7]. This development vastly expanded the substrate scope to include a larger subset of alkyl-substituted allylic alcohols (Scheme 1, top); the relative and absolute stereochemical configurations of all resulting bromochlorides have been assigned and are shown for the (R,S) Schiff base ligand [7–9]. Furthermore, the reaction conditions could now be modulated to affect both catalytic enantioselective dichlorination and dibromination of allylic alcohols [9]. The utility of this method has been demonstrated by highly selective total syntheses of several important polyhalogenated natural product targets including (+)-halomon [8] and (−)-danicalipin A [9].

View Article: PubMed Central - HTML - PubMed

ABSTRACT

The scope of a recently reported method for the catalytic enantioselective bromochlorination of allylic alcohols is expanded to include a specific homoallylic alcohol. Critical factors for optimization of this reaction are highlighted. The utility of the product bromochloride is demonstrated by the first total synthesis of an antibacterial polyhalogenated monoterpene, (−)-anverene.

No MeSH data available.