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. 2023 May;55(10):1487-1496.
doi: 10.1055/s-0042-1751420. Epub 2023 Feb 20.

Carbonyl Allylation and Crotylation: Historical Perspective, Relevance to Polyketide Synthesis, and Evolution of Enantioselective Ruthenium-Catalyzed Hydrogen Auto-Transfer Processes

Eliezer Ortiz  1 , Connor Saludares  1 , Jessica Wu  1 , Yoon Cho  1 , Catherine G Santana  1 , Michael J Krische  1
Affiliations

Carbonyl Allylation and Crotylation: Historical Perspective, Relevance to Polyketide Synthesis, and Evolution of Enantioselective Ruthenium-Catalyzed Hydrogen Auto-Transfer Processes

Eliezer Ortiz et al. Synthesis (Stuttg). 2023 May.

Abstract

The evolution of methods for carbonyl allylation and crotylation of alcohol proelectrophiles culminating in the design of iodide-bound ruthenium-JOSIPHOS catalysts is prefaced by a brief historical perspective on asymmetric carbonyl allylation and its relevance to polyketide construction. Using gaseous allene or butadiene as precursors to allyl- or crotylruthenium nucleophiles, respectively, new capabilities for carbonyl allylation and crotylation have been unlocked, including stereo- and site-selective methods for the allylation and crotylation of 1,3-diols and related polyols.

Keywords: Allene; Allylation; Butadiene; Feedstock; Polyketide; Ruthenium.

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Conflict of interest statement

Conflict of Interest There are no conflicts to declare.

Figures

Figure 1
Figure 1
Selected milestones in carbonyl allylation from racemic reactions to catalytic enantioselective processes.
Figure 2
Figure 2
Selected FDA-approved polyketides medicines often comprise recurring acetate and propionate motifs.
Figure 3
Figure 3
“Borrowing H2” vs H2 auto-transfer.
Figure 4
Figure 4
Stereospecific carbonyl crotylation.
Figure 5
Figure 5
Iodide directs stereogenicity at ruthenium.
Figure 6
Figure 6
Enantioselective entry to polyketide motifs via ruthenium-catalyzed hydrogen auto-transfer.
Scheme 1
Scheme 1
Dienes as allylmetal pronucleophiles in ruthenium-catalyzed carbonyl addition via hydrogen auto-transfer.
Scheme 2
Scheme 2
syn-Diastereo- and enantioselective crotylation of primary alcohols mediated by a 2-silyl-substituted butadiene.
Scheme 3
Scheme 3
Chiral phosphate counterion-dependent inversion of diastereoselectivity in the enantioselective crotylation of primary alcohols mediated by butadiene.
Scheme 4
Scheme 4
Stereo- and site-selective ruthenium-JOSIPHOS catalyzed crotylation of primary alcohols mediated by butadiene.
Scheme 5
Scheme 5
Stereo- and site-selective ruthenium-JOSIPHOS catalyzed allylation of primary alcohols mediated by allene.
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