1,4-Addition of aryl boronic acids to α,β-unsaturated ketones catalyzed by a CCC–NHC pincer rhodium complex

Reilly, Sean W.; Box, Hannah K.; Kuchenbeiser, Glenn; Rubio, Ramel J.; Letko, Christopher S.; Cousineau, Kandarpa D.; Hollis, T. Keith

doi:10.1016/j.tetlet.2014.09.107

Cited by 18 publications

(4 citation statements)

References 75 publications

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“…Similar Pd complexes were synthesized by C–H bond activation . Hollis and co-workers found that Zr(NMe 2 ) 4 was a suitable precursor for the CCC-Zr complex containing ligand D , which was used in the preparation of the first CCC-Ir, -Rh, and -Pt complexes . The CCC-Rh complex was found to serve as a good catalyst in intramolecular hydroamination and conjugate addition of arylboronic acids to α,β-unsaturated ketones. , Braunstein and co-workers reported the direct preparation of CCC-Ir complexes by C–H bond activation of bis(imidazolium) ligand precursors .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of NHC-Oxazoline Pincer Complexes of Rh and Ru and Their Catalytic Activity for Hydrogenation and Conjugate Reduction

et al. 2016

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We describe the preparation and catalytic reactions of new CCN pincer Rh and Ru complexes containing NCH-oxazoline hybrid ligands. Oxazolinyl-phenyl-imidazolium derivatives (3) were suitable ligand precursors for the CCN pincer scaffold. C−H bond activation of 3 with RhCl 3 • 3H 2 O in the presence of NEt 3 yielded the desired CCN pincer Rh complexes 5 in 13−27% yields. The related CCN pincer Ru complexes 8−10 were synthesized in good yields by C−H bond activation of p-cymene Ru complexes 7 in the presence of NaOAc in DMF. The chiral complexes 8 and 9 had two diastereomers according to the coordination of CO and OAc ligands.The CCN Rh complexes showed catalytic activity for conjugate reduction of ethyl β-methylcinnamate with hydrosilane, with moderate enantioselectivity. The CCN Ru complexes were found to be active in the hydrogenation of aromatic ketones. In particular, hydrogenation of 9-acetylanthracene took place at not only the CO bond but also the anthracene ring. The Ru complexes were also used as catalysts in the transfer hydrogenation of 9-acetylanthracene with 2-propanol; again, both the CO bond and the anthracene ring were hydrogenated.

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Section: Introductionmentioning

confidence: 99%

Synthesis of NHC-Oxazoline Pincer Complexes of Rh and Ru and Their Catalytic Activity for Hydrogenation and Conjugate Reduction

et al. 2016

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“…Inspired by their initial work on rhodium‐catalyzed 1,4‐addition of aryl boronic acids to α,β‐unsaturated ketones, and aldehydes, [102] recently the Hollis group reported the first example of CCC‐NHC pincer rhodium‐complex catalyzed β‐borylation of cyclic and acyclic enones (Scheme 19c) [103] . Substrates with alkyl and aryl group at β‐position can easily be borylated and furnish the tertiary and quaternary boron‐substituted product in good yield.…”

Section: Rhodium Catalyzed β‐Borylationmentioning

confidence: 99%

Development of Methods to the Synthesis of β‐Boryl Acyls, Imines and Nitriles

Das

Mahato

Hazra

et al. 2022

The Chemical Record

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Organoboron compounds are highly important and versatile synthetic intermediates for the preparation of a wide range of organic molecules. Organoboron compounds have drawn significant attention among organic chemists due to their Lewis acidic property, non-toxicity, and commercial availability. Over the last several decades, there has been a substantial development of new organoboron compounds, useful in organic synthesis. Among all other organoboron compounds, β-boryl carbonyl compounds are the important ones. The β-boryl compounds have appeared as promising intermediates for various synthetic transformations. The 1,4-conjugate addition of diboron reagents to carbon-carbon double bond in the presence of different transition-metal catalysts has been extensively reported by various research groups across the globe. This mini-review outlines the numerous racemic as well as asymmetric β-borylation methods developed to date.

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“…Furthermore, the processes employ sulfinamido-olefin ligand L69 bearing a sulfinyl sulfur as the only stereogenic center as catalyst precursor, which can be obtained in one step on a multigram scale from a sugar-derived sulfinate ester (Scheme 135). [258][259][260][261] To further uncover the scope of the reaction, the stereoselective 1,4-additions of other arylboronic acids bearing electron donating or withdrawing substituents 2 to N-Me-maleimide 38a were conducted at 0 or À10°C (Table 86). Although the reactions of arylboronic acids required longer reaction times to complete in comparison with those of 2 (=PhB(OH) 2 ), the yields and enantioselectivities of product 264 were over 90%, even when just 0.5 mol of % Rh/(R)-L27 were utilized.…”

Section: Table 48mentioning

confidence: 99%

Rh-catalyzed asymmetric 1,4-addition reactions to α,β-unsaturated carbonyl and related compounds: an update

Heravi

Dehghani

Zadsirjan

2016

Tetrahedron: Asymmetry

109

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Rh-catalyzed asymmetric 1,4-addition reactions to a,b-unsaturated carbonyl and related compounds: an update Available online xxxx Dedicated to my son, OMID on the occasion of his 35th birthday. a b s t r a c tThe Rh-catalyzed asymmetric 1,4-addition of organometallic reagents to an appropriate receptor has been a growing area of research over the last decade. The receptors for such a 1,4-addition reaction are chiefly a,b-unsaturated ketones, esters, amides, enones, nitroalkenes, and occasionally phosphonates etc. This reaction in the presence of chiral rhodium complexes introduce the aryl and alkenyl groups at the b-position of the above electron poor olefins, enantioselectively. Chiral Rh complexes similar to other transition metals can be added to some electron poor olefins, in turn making them viable to attack by various organometallic reagents for highly enantioselective C-C bond formation. The Rh-catalyzed asymmetric 1,4-addition of organometallic reagents to electron poor olefins has been reviewed in 2003. Due to the importance of the asymmetric C-C bond formation via 1,4-conjugate addition reactions and the number of such reactions catalyzed by Rh-complexes, in this review we highlight the recent advances in Rh-complex asymmetric catalyzed 1,4-addition reactions since 2003.

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1,4-Addition of aryl boronic acids to α,β-unsaturated ketones catalyzed by a CCC–NHC pincer rhodium complex

Cited by 18 publications

References 75 publications

Synthesis of NHC-Oxazoline Pincer Complexes of Rh and Ru and Their Catalytic Activity for Hydrogenation and Conjugate Reduction

Synthesis of NHC-Oxazoline Pincer Complexes of Rh and Ru and Their Catalytic Activity for Hydrogenation and Conjugate Reduction

Development of Methods to the Synthesis of β‐Boryl Acyls, Imines and Nitriles

Rh-catalyzed asymmetric 1,4-addition reactions to α,β-unsaturated carbonyl and related compounds: an update

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