Asymmetric Hydroformylation of <i>Z</i>-Enamides and Enol Esters with Rhodium-Bisdiazaphos Catalysts

Abrams, M. Leigh; Foarta, Floriana; Landis, Clark R.

doi:10.1021/ja507701k

Cited by 56 publications

(29 citation statements)

References 44 publications

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“…Although significant progress has been made, full control of regio‐ and stereochemistry can still be problematic . This hampers further functionalization of enol esters in which the stereochemical outcome depends on the double bond geometry (i. e. hydroformylation, hydrogenation). Furthermore, in all transition metal catalyzed enol esterifications, precious metals were used.…”

Section: Methodsmentioning

confidence: 99%

Regio‐ and Stereoselective Chan‐Lam‐Evans Enol Esterification of Carboxylic Acids with Alkenylboroxines

2018

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Efficient and scalable Cu(II)-mediated enol esterification methodology of carboxylic acids from alkenyl boroxines and boronic acids is presented. The reaction shows a wide scope in aliphatic and aromatic carboxylic acids in combination with several alkenyl boroxines. In the case of 2-substituted alkenyl boroxines the double bond configuration was fully retained in the enol ester product. Also N-hydroxyimides and imides could be transformed in the respective amidooxy vinyl enol ethers and vinyl enamides. Finally, with the exception of methionine, all other 19 canonical amino acids showed their compatibility to give the enol esters in a stereoselective fashion.

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Section: Methodsmentioning

confidence: 99%

Regio‐ and Stereoselective Chan‐Lam‐Evans Enol Esterification of Carboxylic Acids with Alkenylboroxines

2018

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“…To date, only very limited examples have been reported in AHF of 1,2-disubstituted alkenes. To address this issue, Tan et al designed the scaffolding catalysis for allyl amines and alcohols 20 , Reek et al used the supramolecular catalysis in AHF of unactivated disubstituted olefins 27 , and in terms of the substrate design, Landis et al successfully achieved AHF of 1,2-disubstituted alkenes comprising ( Z )-enol esters and enamides with Rh-BDP catalysts 11 . Due to electron-withdrawing groups, high regioselectivities were given (up to >99:1) for AHF of ( Z )-enol esters and enamides.…”

Section: Introductionmentioning

confidence: 99%

“…In these examples, CO was mainly incorporated at the α position of the oxygen atom or nitrogen atom (Fig. 1 a) 9 – 11 , 31 – 34 . By contrast, to achieve the AHF on the β position of the heteroatom (O or N) is a tough task.…”

Section: Introductionmentioning

confidence: 99%

Silicon-oriented regio- and enantioselective rhodium-catalyzed hydroformylation

You

Yang

et al. 2018

Nat Commun

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Hydroformylation of 1,2-disubstituted alkenes usually occurs at the α position of the directing heteroatom such as oxygen atom and nitrogen atom. By contrast, to achieve hydroformylation on the β position of the heteroatom is a tough task. Herein, we report the asymmetric rhodium-catalyzed hydroformylation of 1,2-disubstituted alkenylsilanes with excellent regioselectivity at the β position (relative to the silicon heteroatom) and enantioselectivity. In a synthetic sense, we achieve the asymmetric hydroformylation on the β position of the oxygen atom indirectly by using the silicon group as a surrogate for the hydroxyl. Density functional theory (DFT) calculations are carried out to examine energetics of the whole reaction path for Rh/YanPhos-catalyzed asymmetric hydroformylation and understand its regioselectivity and enantioselectivity. Our computational study suggests that the silicon group can activate the substrate and is critical for the regioselectivity.

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“…Enol ester derivatives represent a relevant class of compounds widely used as mild acylating reagents, [1][2][3][4] as monomers for the production of diverse types of polymers and copolymers, [5][6][7][8] and as starting materials in a large variety of reactions, including asymmetric hydrogenation, [9][10][11][12] cycloaddition, [13][14][15][16] cyclization, [17][18][19][20] hydroformylation, [21][22][23] cross-coupling, [24][25][26][27] Michael addition, [28][29][30][31] aldol-type, [32][33][34] Mannich-type 35 and amide bond-forming processes, 36 to name a few. The enol ester motif is also found in a number of natural products with relevant biological properties.…”

Section: Introductionmentioning

confidence: 99%

The intermolecular hydro-oxycarbonylation of internal alkynes: current state of the art

González-Liste¹,

Francos²,

García‐Garrido³

et al. 2017

Arkivoc

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The intermolecular addition of carboxylic acids to alkynes is one of the most straightforward and atomeconomical methods currently available for the preparation of synthetically useful enol esters. However, the vast majority of works have focused on the use of terminal alkynes, substrates much more reactive than their corresponding internal counterparts. In fact, efficient and general protocols for hydro-oxycarbonylation of internal alkynes have only seen the light in recent years. In the present review article an overview of the progress made in the field is given. Catalytic reactions promoted by ruthenium, palladium, silver and gold complexes/salts, along with some specific metal-free protocols, are covered.

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Asymmetric Hydroformylation of Z-Enamides and Enol Esters with Rhodium-Bisdiazaphos Catalysts

Cited by 56 publications

References 44 publications

Regio‐ and Stereoselective Chan‐Lam‐Evans Enol Esterification of Carboxylic Acids with Alkenylboroxines

Regio‐ and Stereoselective Chan‐Lam‐Evans Enol Esterification of Carboxylic Acids with Alkenylboroxines

Silicon-oriented regio- and enantioselective rhodium-catalyzed hydroformylation

The intermolecular hydro-oxycarbonylation of internal alkynes: current state of the art

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