2018
DOI: 10.1002/chem.201803574
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Remote Nucleophilic Allylation by Allylrhodium Chain Walking

Abstract: Metal migration through a carbon chain is a versatile method for achieving remote functionalization. However, almost all known examples involve the overall net migration of alkylmetal species. Here, we report that allylrhodium species obtained from hydrorhodation of 1,3-dienes undergo chain walking toward esters, amides, or (hetero)arenes over distances of up to eight methylene units. The final, more highly conjugated allylrhodium species undergo nucleophilic allylation with aldehydes and with an imine to give… Show more

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Cited by 13 publications
(9 citation statements)
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“…For example, the diester 1 b underwent reaction to give a single coupling product in 73 % yield, chain‐walking and addition adjacent to the remote ester was not observed. Even where there is a clear thermodynamic driving force for isomerization, like in the cases of the ester‐tethered aryl diene 1 c , only direct‐coupling product 2 c is obtained, contrasting the approaches with alternative reducing agents …”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…For example, the diester 1 b underwent reaction to give a single coupling product in 73 % yield, chain‐walking and addition adjacent to the remote ester was not observed. Even where there is a clear thermodynamic driving force for isomerization, like in the cases of the ester‐tethered aryl diene 1 c , only direct‐coupling product 2 c is obtained, contrasting the approaches with alternative reducing agents …”
Section: Resultsmentioning
confidence: 99%
“…The Z ‐selective coupling of aldehydes and dienes can be promoted by Rh‐based catalysts, however the requirement for stoichiometric Et 3 B to generate a Rh‐hydride intermediate limits chemoselectivity . Under these reaction conditions, products derived from chain‐walking isomerization are observed, restricting access to a narrow range of product classes . The lack of generality in Z ‐selective diene additions highlights the difficulty in controlling both site‐ and stereoselectivity in catalytic diene functionalization, particularly in those reactions that generate thermodynamically less favorable product isomers…”
Section: Introductionmentioning
confidence: 99%
“…An emerging strategy in the synthetic chemist’s toolbox is chain walking coupled with remote functionalization, in which a functionality is installed at a certain distance from the original reaction center. Such approaches have gained increasing popularity and significance, as they allow installing functionalities in a fundamentally different manner, and as such, they can potentially unlock compatibility with different functional groups and enable the use of alternative starting materials or even mixtures of olefin precursors. While numerous elegant transformations have been developed, especially C–C, C–Si, and C–B bond formations or redox events (e.g., OH to carbonyl) , as terminating functionalization in this context, to date, there is no precedence of remote functionalization of ketones. …”
Section: Introductionmentioning
confidence: 99%
“…As previously outlined, this transformation provides access to a strategy for the synthesis of otherwise highly challenging asymmetric alcohol products with high ee values. To demonstrate this, we reductively removed the sulfone group [17] from a representative number of products to generate the unsubstituted products 21-25 with high ee values, which in each case was an alcohol with very little steric or electronic difference between the groups flanking it (Figure 9 C). Traditionally such targets would be regarded as very difficult to prepare through direct ketone ATH.…”
Section: Angewandte Chemiementioning
confidence: 99%