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Enantioselective total synthesis of (-)-acylfulvene and (-)-irofulven.

ABSTRACT: We report our full account of the enantioselective total synthesis of (-)-acylfulvene (1) and (-)-irofulven (2), which features metathesis reactions for the rapid assembly of the molecular framework of these antitumor agents. We discuss (1) the application of an Evans Cu-catalyzed aldol addition reaction using a strained cyclopropyl ketenethioacetal, (2) an efficient enyne ring-closing metathesis cascade reaction in a challenging setting, (3) the reagent IPNBSH for a late-stage reductive allylic transposition reaction, and (4) the final RCM/dehydrogenation sequence for the formation of (-)-acylfulvene (1) and (-)-irofulven (2).

SUBMITTER: Siegel DS

PROVIDER: S-EPMC2805080 | biostudies-literature | 2009 Dec

REPOSITORIES: biostudies-literature

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Enantioselective total synthesis of (-)-acylfulvene and (-)-irofulven.

Siegel Dustin S DS Piizzi Grazia G Piersanti Giovanni G Movassaghi Mohammad M

The Journal of organic chemistry 20091201 24

We report our full account of the enantioselective total synthesis of (-)-acylfulvene (1) and (-)-irofulven (2), which features metathesis reactions for the rapid assembly of the molecular framework of these antitumor agents. We discuss (1) the application of an Evans Cu-catalyzed aldol addition reaction using a strained cyclopropyl ketenethioacetal, (2) an efficient enyne ring-closing metathesis cascade reaction in a challenging setting, (3) the reagent IPNBSH for a late-stage reductive allylic ...[more]

PMID: 19938810

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