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. 2010 Mar 17;132(10):3612-20.
doi: 10.1021/ja910804u.

On the stereochemical course of palladium-catalyzed cross-coupling of allylic silanolate salts with aromatic bromides

Scott E Denmark  1 , Nathan S Werner
Affiliations

On the stereochemical course of palladium-catalyzed cross-coupling of allylic silanolate salts with aromatic bromides

Scott E Denmark et al. J Am Chem Soc. .

Abstract

The stereochemical course of palladium-catalyzed cross-coupling reactions of an enantioenriched, alpha-substituted, allylic silanolate salt with aromatic bromides has been investigated. The allylic silanolate salt was prepared in high geometrical (Z/E, 94:6) and high enantiomeric (94:6 er) purity by a copper-catalyzed S(N)2' reaction of a resolved allylic carbamate. Eight different aromatic bromides underwent cross-coupling with excellent constitutional site-selectivity and excellent stereospecificity. Stereochemical correlation established that the transmetalation event proceeds through a syn S(E)' mechanism which is interpreted in terms of an intramolecular delivery of the arylpalladium electrophile through a key intermediate that contains a discrete Si-O-Pd linkage.

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Figures

Figure 1
Figure 1
General classification of asymmetric transition metal-catalyzed cross-coupling reactions.
Figure 2
Figure 2
Stereochemical control elements in SE’ reactions (CIP: E > CH=CH > R1).
Figure 3
Figure 3
Synthetic Strategy to Determine the Stereochemical Course of Transmetalation.
Figure 4
Figure 4
Possible pathways for the transmetalation of allylic silanolates. (R = i-Bu, RE = reductive elimination).
Figure 5
Figure 5
Refined catalytic cycle.
Scheme 1<sup>a</sup>
Scheme 1a
Scheme 2
Scheme 2
Scheme 3
Scheme 3
Scheme 4
Scheme 4
Scheme 5
Scheme 5
Scheme 6
Scheme 6
Scheme 7<sup>a</sup>
Scheme 7a
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References

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    1. The trivial case of cross-coupling of chiral subunits where the newly formed carbon–carbon bond is not a stereogenic unit are excluded.

    1. By far the largest category of transition metal-catalyzed, carbon-carbon and carbon-heteroatom bond forming reactions involves the asymmetric capture of π-allyl-metals derived from palladium, molybdenum, rhodium and iridium with a wide range of nucleophiles. These powerful reactions have been thoroughly reviewed and therefore will not be categorized here, see: Lu Z, Ma S. Angew. Chem., Int. Ed. 2008;47:258–297. Trost BM, Crawley ML. Chem. Rev. 2003:2921–2943. Pfaltz A, Lautens M. Chapt. 24. In: Jacobsen EN, Pfaltz A, Yamamoto H, editors. Comprehensive Asymmetric Catalysis. Vol. II. Heidelberg: Springer Verlag; 1999.

    1. For a definition of internal and external selection see: Denmark SE, Almstead NG. Allylation of Carbonyls: Methodology and Stereochemistry. In: Otera J, editor. Modern Carbonyl Chemistry. Weinheim: Wiley–VCH; 2000. pp. 299–402.

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