Palladium‐Catalyzed Enantioselective Allylic Alkylations through C–H Activation

Trost, Barry M.; Thaisrivongs, David A.; Donckèle, Etienne J.

doi:10.1002/anie.201207870

Cited by 133 publications

(70 citation statements)

References 42 publications

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“…The compatibility of phosphine based ligands being capable of serving in oxidative allylic alkylations led to the development of an asymmetric version as well (eq 85). 85 This example is the only reported asymmetric allylic alkylation of any kind involving allylic C-H activation.…”

Section: Oxidative Allylic Alkylationmentioning

confidence: 87%

Metal catalyzed allylic alkylation: its development in the Trost laboratories

Trost

2015

Tetrahedron

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190

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Section: Oxidative Allylic Alkylationmentioning

confidence: 87%

Metal catalyzed allylic alkylation: its development in the Trost laboratories

Trost

2015

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190

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“…[3] Alternatively, chiral palladium/phosphoramidite catalysts for allylic C–H functionalizations have demonstrated modest enantioselectivity (avg. 75% ee, 1 example ≥90% ee [4] , avg. 83% ee, 2 examples at 90% ee [5] ), limited olefin scope (generally doubly activated C–H bonds) and high sensitivity to O 2 .…”

mentioning

confidence: 99%

“…83% ee, 2 examples at 90% ee [5] ), limited olefin scope (generally doubly activated C–H bonds) and high sensitivity to O 2 . [4,5] We hypothesized the ideal catalytic platform would utilize an oxidatively stable, chiral ligand capable of promoting both C–H cleavage and functionalization, thus circumventing the challenges of serial ligand catalysis.…”

mentioning

confidence: 99%

“…Gratifyingly, broad aromatic substitution is tolerated, with both electron-rich substrates (entries 2b , 2c , 2d ) and electron-deficient substrates (entries 2e , 2f , 2g , 2h , 2i ) furnishing the desired products in good yields and high enantioselectivities. Broad tolerance for electronic substitution on aryls has not been previously shown for other asymmetric allylic C–H methods, which show either decreased enantioselectivity for electron-rich aryl moieties, [4] or inconsistent trends for aryl tolerance. [5] Bromide and chloride substitution is well tolerated, and these groups serve as handles for further manipulation (products 2e , 2h ).…”

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confidence: 99%

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Enantioselective Allylic C−H Oxidation of Terminal Olefins to Isochromans by Palladium(II)/Chiral Sulfoxide Catalysis

2016

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The enantioselective synthesis of isochroman motifs has been accomplished via Pd(II)-catalyzed allylic C–H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C–H oxidation reaction proceeds with the broadest scope and highest levels asymmetric induction reported to date (avg. 92% ee, 13 examples ≥90% ee)

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“…The stereochemical complexity of medicinally important compounds is increasing, and recent studies have suggested that compounds containing increased numbers of sp 3 carbon centers are more successful through clinical trials. 1 Although C-H bond functionalization reactions have the potential to alter the strategies by which these compounds are prepared, 2 a major challenge encountered when developing C-H bond functionalization reactions is the control of absolute and relative stereochemistry.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Functionalization of Allylic C–H Bonds Following a Strategy of Functionalization and Diversification

Sharma

Hartwig

2013

J. Am. Chem. Soc.

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We report the enantioselective functionalization of allylic C-H bonds in terminal alkenes by a strategy involving the installation of a temporary functional group at the terminal carbon atom by C-H bond functionalization, followed by diversification of this intermediate with a broad scope of reagents. The method consists of a one-pot sequence of palladium-catalyzed allylic C-H bond oxidation under neutral conditions to form linear allyl benzoates, followed by iridium-catalyzed allylic substitution. This overall transformation forms a variety of chiral products containing a new C-N, C-O, C-S or C-C bond at the allylic position in good yield with high branched-to-linear selectivity and excellent enantioselectivity (ee ≤ 97%). The broad scope of the overall process results from separating the oxidation and functionalization steps; by doing so, the scope of nucleophile encompasses those sensitive to direct oxidative functionalization. The high enantioselectivity of the overall process is achieved by developing an allylic oxidation that occurs without acid to form the linear isomer with high selectivity. These allylic functionalization processes are amenable to an iterative sequence leading to (1,n)-functionalized products with catalyst-controlled diastereo- and enantioselectivity. The utility of the method in the synthesis of biologically active molecules has been demonstrated.

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Palladium‐Catalyzed Enantioselective Allylic Alkylations through C–H Activation

Cited by 133 publications

References 42 publications

Metal catalyzed allylic alkylation: its development in the Trost laboratories

Metal catalyzed allylic alkylation: its development in the Trost laboratories

Enantioselective Allylic C−H Oxidation of Terminal Olefins to Isochromans by Palladium(II)/Chiral Sulfoxide Catalysis

Enantioselective Functionalization of Allylic C–H Bonds Following a Strategy of Functionalization and Diversification

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