Enantioselective Rh(I)-Catalyzed Cyclization of Arylboron Compounds onto Ketones

Low, Darryl W.; Pattison, Graham; Wieczysty, Martin D.; Churchill, Gwydion H.; Lam, Hon Wai

doi:10.1021/ol300845q

Cited by 71 publications

(29 citation statements)

References 55 publications

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“…As we are active in this eld, 12 and aer considering previous literature work [13][14][15] we set out to study the hitherto unknown Scheme 1 Synthetic route to the isoquinolin-1(2H)-one derivatives obtained in this work.…”

Section: Resultsmentioning

confidence: 99%

“…12h, 23 As far as we are aware, no reports on the intramolecular addition of metal aryl species to aldehydes have been reported to date. [13][14][15] We started our study with (3a) applying literature conditions 24 with Rh, Pd and Cu catalysts.…”

Section: Resultsmentioning

confidence: 99%

“…Plates were visualized either by UV light or with phosphomolybdic acid in ethanol. 1 H and 13 C NMR spectra was recorded on a Bruker Avance III at 400 and 100 MHz, respectively, and the chemical shis were quoted in parts per million (ppm) referenced to the appropriate non-deuterated solvent peak relative to 0.0 ppm for tetramethylsilane. Mass spectra (MS) using the ESI-TOF technique were obtained from the University of Vigo, C.A.C.T.I., Spain.…”

Section: General Considerationsmentioning

confidence: 99%

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Transition-metal-catalyzed intramolecular cyclization of amido(hetero)arylboronic acid aldehydes to isoquinolinones and derivatives

2015

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We report an innovative and simple three step high yielding synthesis of a library of 14 chiral isoquinolinone and azepinone derivatives with benzyl, pyridyl and thiophene cores starting from amidoarylboronic acid aldehydes. These products have potential for treating neurodegenerative diseases. The key reaction in this synthetic pathway was an efficient metal-catalyzed (with Rh, Cu and Pd catalysts) intramolecular cyclization. A maximum yield of 87% was obtained using a Rh(I) catalyst.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: General Considerationsmentioning

confidence: 99%

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Transition-metal-catalyzed intramolecular cyclization of amido(hetero)arylboronic acid aldehydes to isoquinolinones and derivatives

2015

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“…Lam and co-workers successfully realized the Rh-catalyzed intramolecular cyclization of arylboron compounds 92 with S/olefin ligand 68 b to produce a variety of the tetrahydroisoquinolin-4-ols 93 in 70-96 % yields and 80-92 % ee (Scheme 28). [46] Very recently, Du and co-workers found that chiral S/ olefin ligand 70 b was highly efficient in Rh-catalyzed formal [3+2] cycloaddition between racemic butadiene monoxide 94 and imines 95 and 97.…”

Section: Chiral S/olefin Hybrid Ligandsmentioning

confidence: 99%

Synthesis of Chiral Olefin Ligands and their Application in Asymmetric Catalysis

Feng

2012

Asian J Org Chem

128

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Chiral olefins have recently emerged as among the most promising ligands for asymmetric catalysis. In the past nearly ten years, significant advances have been made in developing ligands, including diene and heteroatom/olefin hybrid ligands, and exploring their applications in challenging metal-catalyzed asymmetric reactions. Especially in some cases, chiral olefin ligands have an obvious advantage over some conventional chiral ligands in terms of activity and selectivity. Besides the most often studied rigidly bicyclic dienes, readily accessible chiral-chain dienes with flexible frameworks and two terminal olefins as coordinating groups have also proven to be effective for achieving high levels of enantioselectivity in transition-metal-catalyzed asymmetric reactions. Moreover, the terminal olefins can be combined with phosphorus atoms on suitable chiral skeletons for the development of novel phosphorus/olefin (P/olefin) hybrid ligands, which have high activity and selectivity in Pd-catalyzed asymmetric transformations. Significantly, sulfur/olefin (S/olefin) hybrid ligands have been successfully explored and applied in a range of Rh-catalyzed asymmetric transformations. This Focus Review will mainly discuss the synthesis of recently developed chiral-chain diene ligands, phosphorus/terminal-olefin hybrid ligands, and sulfur/olefin hybrid ligands, and their application in asymmetric catalysis.

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“…Among the various methods, [3] thec atalytic asymmetric arylations of ketones stand out to be most attractive. Despite the recent advances in asymmetric additions of arylboron reagents to aldehydes, [6] activated ketones, [7] or ketones in an intramolecular fashion, [8] few successful results were reported on asymmetric intermolecular addition of aryl boron reagents to simple ketones. Despite the recent advances in asymmetric additions of arylboron reagents to aldehydes, [6] activated ketones, [7] or ketones in an intramolecular fashion, [8] few successful results were reported on asymmetric intermolecular addition of aryl boron reagents to simple ketones.…”

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confidence: 99%

Highly Enantioselective Rhodium‐Catalyzed Addition of Arylboroxines to Simple Aryl Ketones: Efficient Synthesis of Escitalopram

et al. 2016

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Highly enantioselective additions of arylboroxines to simple aryl ketones have been achieved for the first time with aR h/(R,R,R,R)-WingPhos catalyst, thus providing ar ange of chiral diaryl alkylcarbinols with excellent ee values and yields. (R,R,R,R)-WingPhos has been proven to be crucial for the high reactivity and enantioselectivity.The method has enabled an ew,c oncise,a nd enantioselective synthesis of the antidepressant drug escitalopram.Chiral diaryl alkyl carbinol moieties exist in an umber of therapeutic agents and natural products, [1] such as the antidepressant escitalopram, [2a] antihistamine clemastine, [2b] cough suppressant chlophedianol, [2c] multi-AGC kinase inhibitor AT13148, [2d] fungicide flutriafol, [2e] and lignan hydroxyotobain [2f] (Figure 1). Thee fficient synthesis of these chiral tertiary alcohols have thus gained ag reat deal of attention. Among the various methods, [3] thec atalytic asymmetric arylations of ketones stand out to be most attractive. [4,5] In particular,a symmetric addition of nontoxic,s table,a nd operationally simple aryl boron reagents to simple unactivated ketones is highly desirable yet remains challenging. Despite the recent advances in asymmetric additions of arylboron reagents to aldehydes, [6] activated ketones, [7] or ketones in an intramolecular fashion, [8] few successful results were reported on asymmetric intermolecular addition of aryl boron reagents to simple ketones.[9] Low enantioseletivities were reported for either chiral nickel or rhodium catalysts (a Ni/chiral N-heterocyclic carbene ligand:3 6% ee,[9a] aR h/ chiral bisphosphine:38%ee, [9b] aRh/chiral diene:68% ee).[9c]Al ow yield was also observed in our previous study,a lbeit with an improved enantioselectivity (25 %y ield, 95 % ee).[7l]To our knowledge,b oth excellent enantioselectivities and yields are yet to be achieved for intermolecular asymmetric additions of aryl boron reagents to simple ketones.Herein we report ah ighly enantioselective rhodium-catalyzed addition of arylboroxines to simple aryl ketones in excellent yields and with up to 99 % ee by using Rh/(R,R,R,R)-WingPhos as the catalyst. This method has enabled an efficient and concise synthesis of the blockbuster antidepressant escitalopram. Ligand design has played ac entral role in the development of efficient metal-catalyzed reactions.[10] Thed esign of chiral phosphorus ligands capable of long-range stereocontrol remain asignificant challenge with limited success.Because of the less reactive nature and low coordinative ability of simple ketones,i nc omparison with aldehydes or imines,t he intermolecular addition of arylboron reagents to simple ketones relies upon the metal catalyst to bring the two reaction partners into close proximity,a sw ell as provide good stereocontrol at ag reater distance from the metal center (Figure 2). Am etal catalyst equipped with ad iphosphine ligand having as hallow chiral pocket (Figure 2a)w ill be inefficient for such ar eaction in terms of both enantioselectivity and reactivit...

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Enantioselective Rh(I)-Catalyzed Cyclization of Arylboron Compounds onto Ketones

Cited by 71 publications

References 55 publications

Transition-metal-catalyzed intramolecular cyclization of amido(hetero)arylboronic acid aldehydes to isoquinolinones and derivatives

Transition-metal-catalyzed intramolecular cyclization of amido(hetero)arylboronic acid aldehydes to isoquinolinones and derivatives

Synthesis of Chiral Olefin Ligands and their Application in Asymmetric Catalysis

Highly Enantioselective Rhodium‐Catalyzed Addition of Arylboroxines to Simple Aryl Ketones: Efficient Synthesis of Escitalopram

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