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Hydrodealkenylative C(sp3)-C(sp2) bond fragmentation.

ABSTRACT: Chemical synthesis typically relies on reactions that generate complexity through elaboration of simple starting materials. Less common are deconstructive strategies toward complexity-particularly those involving carbon-carbon bond scission. Here, we introduce one such transformation: the hydrodealkenylative cleavage of C(sp3)-C(sp2) bonds, conducted below room temperature, using ozone, an iron salt, and a hydrogen atom donor. These reactions are performed in nonanhydrous solvents and open to the air; reach completion within 30 minutes; and deliver their products in high yields, even on decagram scales. We have used this broadly functionality tolerant transformation to produce desirable synthetic intermediates, many of which are optically active, from abundantly available terpenes and terpenoid-derived precursors. We have also applied it in the formal total syntheses of complex molecules.

SUBMITTER: Smaligo AJ

PROVIDER: S-EPMC6625654 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

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Hydrodealkenylative C(sp3)-C(sp2) bond fragmentation.

Smaligo Andrew J AJ Swain Manisha M Quintana Jason C JC Tan Mikayla F MF Kim Danielle A DA Kwon Ohyun O

Science (New York, N.Y.) 20190501 6441

Chemical synthesis typically relies on reactions that generate complexity through elaboration of simple starting materials. Less common are deconstructive strategies toward complexity-particularly those involving carbon-carbon bond scission. Here, we introduce one such transformation: the hydrodealkenylative cleavage of C(sp3)-C(sp2) bonds, conducted below room temperature, using ozone, an iron salt, and a hydrogen atom donor. These reactions are performed in nonanhydrous s ...[more]

PMID: 31097667

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