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Matyushenkov, E. A.; Churikov, D. G.; Соколов, Н. А.; Kulinkovich, O. G.

doi:10.1023/a:1026047515568

Russian Journal of Organic Chemistry

2003

DOI: 10.1023/a:1026047515568

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E. A. Matyushenkov

D. G. Churikov

Н. А. Соколов

et al.

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Cited by 7 publications

(1 citation statement)

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“…In short, preassociation of the allylic alkoxide with a preformed titanacyclopropane (derived from the vinylsilane) produces an intermediate mixed titanate ester capable of rearrangement via formal metallo-[3,3]-rearrangement . While the C−C bond formation proceeds with allylic transposition, stereochemical control is thought to derive from minimization of nonbonded steric interactions in a boatlike conformation (i.e., A′ and B′ ) where the σ C−Ti bond is aligned with the π CC bond …”

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Conversion of Allylic Alcohols to Stereodefined Trisubstituted Alkenes: A Complementary Process to the Claisen Rearrangement

Belardi

Micalizio

2008

J. Am. Chem. Soc.

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A stereoselective method for the conversion of allylic alcohols to (Z)-trisubstituted alkenes is presented. Overall, the reaction sequence described is stereochemically complimentary to related Claisen rearrangement reactions -processes that typically deliver the stereoisomeric trisubstituted alkene containing products.Methods for the synthesis of geometrically defined trisubstituted olefins define a pillar of modern synthetic organic chemistry. From a target-based perspective, these stereodefined structural motifs are ubiquitous in natural products and molecules of biomedical and physical relevance (Figure 1). From a reactivity-based perspective, geometrically defined olefins serve as a foundation for stereoselective synthesis. These factors have driven the invention of a large variety of chemical methods for the convergent synthesis of stereodefined olefins. While many of these methods proceed from carbonyl addition chemistry or alkyne functionalization, the use of allylic alcohol derivatives in sigmatropic processes defines a powerful means to access a subset of stereodefined polysubstituted olefins. 1 Of these, Claisen-based methods have been particularly effective at establishing stereodefined (E)-trisubstituted olefins. Here, we describe a metal-mediated reductive cross-coupling reaction that defines a stereochemically complimentary means of converting allylic alcohols to products related to those derived from Claisen rearrangement (Figure 2). While describing a unique stereoselective transformation for complex molecule synthesis, this study also defines a novel reductive cross-coupling reaction between alkenes and allylic alcohols. 2,3 Recently, we demonstrated that allylic alcohols are useful substrates in titanium-mediated reductive cross-coupling reactions with internal alkynes. 4 In these reactions, 1,4-dienes result from C-C bond formation between preformed titanium-alkyne complexes and allylic alkoxides. While quite useful for the stereoselective synthesis of substituted 1,4-dienes, we wondered whether a related reductive cross-coupling process could define a stereoselective convergent pathway to isolated di-and trisubstituted olefins. To accomplish such a glenn.micalizio@yale.edu. Our initial studies, depicted in Figure 3, provided some hope that the desired stereoselective transformation would be possible. In general, the preformed lithium alkoxide of an allylic alcohol was combined with vinyltrimethylsilane in Et 2 O, cooled and treated with the combination of ClTi(Oi-Pr) 3 and C 5 H 9 MgCl (−78 to 0 °C). 6 While cross-coupling of allylic alkoxides 1 and 4 with vinyltrimethylsilane (2) provided cross-coupled products 3 and 5 in 58-66% yield, these reactions proceeded without stereoselection (E:Z = 1:1). In contrast, reductive cross-coupling of the (Z)-disubstituted alkene 6 with 2 provided the (E)-alkene 7 in 64% (E:Z = 9:1). Highest levels of (E)-selectivity were observed in the reaction of 8 with 2. This process provided 9 in 69% yield with ≥20:1 selectivity; defining a stereoselective...

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mentioning

confidence: 99%

Conversion of Allylic Alcohols to Stereodefined Trisubstituted Alkenes: A Complementary Process to the Claisen Rearrangement

Belardi

Micalizio

2008

J. Am. Chem. Soc.

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Stereoselective Alkylation of Allylic Alcohols: Tandem Ethylation and Functionalization

2011

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Stereoselective Alkylation of Allylic Alcohols: Tandem Ethylation and Functionalization

2011

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Cited by 7 publications

References 12 publications

Conversion of Allylic Alcohols to Stereodefined Trisubstituted Alkenes: A Complementary Process to the Claisen Rearrangement

Conversion of Allylic Alcohols to Stereodefined Trisubstituted Alkenes: A Complementary Process to the Claisen Rearrangement

Stereoselective Alkylation of Allylic Alcohols: Tandem Ethylation and Functionalization

Stereoselective Alkylation of Allylic Alcohols: Tandem Ethylation and Functionalization

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