Abstract
The Petasis boron–Mannich reaction, simply referred to as the Petasis reaction, is a powerful multicomponent coupling reaction of a boronic acid, an amine, and a carbonyl derivative. Highly functionalized amines with multiple stereogenic centers can be efficiently accessed via the Petasis reaction with high levels of both diastereoselectivity and enantioselectivity. By drawing attention to examples reported in the past 8 years, this Review demonstrates the breadth of the reactivity and synthetic applications of Petasis reactions in several frontiers: the expansion of the substrate scope in the classic three-component process; nonclassic Petasis reactions with additional components; Petasis-type reactions with noncanonical substrates, mechanism, and products; new asymmetric versions assisted by chiral catalysts; combinations with a secondary or tertiary transformation in a cascade- or sequence-specific manner to access structurally complex, natural-product-like heterocycles; and the synthesis of polyhydroxy alkaloids and biologically interesting molecules.
Highlights
A Petasis reaction (PR)−RCM sequence was employed for the synthesis of highly functionalized pyrrolinols 240 featuring a Grubbs-IIcatalyzed ring-closing metathesis reaction of the Petasis products 239 synthesized from tert-butyldiphenylsilyl-protected α-hydroxyl aldehydes, substituted allylamines, and Review (E)-styrylboronic acid with excellent diastereoselectivity and retained enantiomeric purity
This Review revealed the breadth of the synthetic application and the recent progress in employing the PR through a systematic overview of examples published in the past 8 years
The reactivity of the PR has been greatly explored in different frontiers, as demonstrated by illustrated recent examples, which addressed the two limitations and significantly expanded the utility of the PR in organic synthesis, medicinal chemistry, and chemical biology
Summary
Multicomponent reactions (MCRs),[1−3] such as those that bear the name of their discoverers, Biginelli,[4] Hantzsch,[5] Mannich,[6] Passerini,[7] Povarov,[8] Strecker,[9] and Ugi,[10,11] have been widely used as complexity-generating reactions to rapidly access diverse scaffolds of both synthetic and biological interest. The “Petasis” notation has been applied to several other transformations, such as the Petasis olefination reaction reported in 199014 and the Petasis−Ferrier rearrangement reported in 1996.15 The former is a ketone or aldehyde olefination via a four-membered titanium intermediate using dimethyl titanocene as the Petasis reagent,[14] and the latter is a transformation of cyclic enol acetals to tetrahydrofurans or tetrahydropyrans via a Lewis-acid-promoted oxygen-to-carbon transposition pathway.[15] the original PR did not employ any catalyst, variants relying on either chiral organocatalysts or metal complexes are widely abundant, together with reactions where the original three components, amine, aldehyde, and boronic acid, have been expanded to include many other functionalities In this Review, the abbreviation “PR” refers to boron-based reactions as well as the above-mentioned variants. Review including the synthesis of fluorous-tagged N-alkylated amino acids using fluorous-tagged hydroxylamines,[47,48] derivatization and stapling of peptides by an on-resin PR,[49] and combinatorial synthesis of peptidomimetics employing PRUgi sequence reactions,[50] but such solid-supported PRs are generally not covered in this Review
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