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. 2011 Jul 13;133(27):10582-6.
doi: 10.1021/ja2046028. Epub 2011 Jun 16.

Diastereo- and enantioselective ruthenium-catalyzed hydrohydroxyalkylation of 2-silyl-butadienes: carbonyl syn-crotylation from the alcohol oxidation level

Jason R Zbieg  1 , Joseph Moran, Michael J Krische
Affiliations

Diastereo- and enantioselective ruthenium-catalyzed hydrohydroxyalkylation of 2-silyl-butadienes: carbonyl syn-crotylation from the alcohol oxidation level

Jason R Zbieg et al. J Am Chem Soc. .

Abstract

Exposure of alcohols 2a-2j to 2-silyl-butadienes in the presence of ruthenium complexes modified by (R)-SEGPHOS or (R)-DM-SEGPHOS results in redox-triggered generation of allylruthenium-aldehyde pairs, which combine to form products of carbonyl crotylation 4a-4j in the absence of stoichiometric byproducts and with high levels of syn-diastereo- and enantioselectivity. In the presence of isopropanol under otherwise identical conditions, aldehydes 3a-3j are converted to an equivalent set of adducts 4a-4j. Whereas reactions conducted using conventional heating require 48 h, microwave irradiation enables full conversion in only 4 h. Finally, as illustrated in the conversion of adduct 4a to compounds 6a and 6b, diastereoselective hydroboration-Suzuki cross-coupling with aryl and vinyl halides followed by Fleming-Tamao oxidation enables generation of anti,syn-stereotriads found in numerous polyketide natural products.

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Figures

Figure 1
Figure 1
syn-Diastereo- and Enantioselective carbonyl crotylation in the absence of stoichiometric byproducts via ruthenium catalyzed hydrohydroxyalkylation of 2-silyl-butadienes
Figure 2
Figure 2
Stereochemical model for 2-silyl-butadiene mediated syn-crotylation employing a (R)-DM-SEGPHOS modified ruthenium catalyst.a
Scheme 1
Scheme 1
Diastereoselective hydroboration enables formation of anti,syn-stereotriads.
Scheme 2
Scheme 2
Proposed catalytic mechanism for ruthenium catalyzed diene hydrohydroxymethylation as supported by established stoichiometric transformations.
See this image and copyright information in PMC

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