Rhodium-Catalyzed Asymmetric Synthesis of Indanones:  Development of a New “Axially Chiral” Bisphosphine Ligand

Shintani, Ryo; Yashio, Keiji; Nakamura, Tomoaki; Okamoto, Kazuhiro; Shimada, Toyoshi; Hayashi, Tamio

doi:10.1021/ja056584s

Cited by 75 publications

(18 citation statements)

References 22 publications

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“…The same research group has proposed another asymmetric isomerization of racemic alcohols 161 leading to the formation of 1-indanones 162 [77]. In this reaction, β-chiral 1-indanones 162 were obtained by isomerization of racemic α-arylpropargyl alcohols 161 in the presence of a rhodium catalyst.…”

Section: Reviewmentioning

confidence: 99%

Synthesis of 1-indanones with a broad range of biological activity

Turek¹,

Szczęsna²,

Koprowski³

et al. 2017

Beilstein J. Org. Chem.

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This comprehensive review describes methods for the preparation of 1-indanones published in original and patent literature from 1926 to 2017. More than 100 synthetic methods utilizing carboxylic acids, esters, diesters, acid chlorides, ketones, alkynes, alcohols etc. as starting materials, have been performed. This review also covers the most important studies on the biological activity of 1-indanones and their derivatives which are potent antiviral, anti-inflammatory, analgesic, antimalarial, antibacterial and anticancer compounds. Moreover, they can be used in the treatment of neurodegenerative diseases and as effective insecticides, fungicides and herbicides.

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Section: Reviewmentioning

confidence: 99%

Synthesis of 1-indanones with a broad range of biological activity

Turek¹,

Szczęsna²,

Koprowski³

et al. 2017

Beilstein J. Org. Chem.

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“…Diphosphanes with general structure A (Scheme 1) employing a 1,1Ј-biphenyl-2,2Ј-diyl bridge have attracted much interest as supporting ligands in numerous transition-metalcatalyzed transformations, [1][2][3] including Suzuki-Miyaura cross coupling reactions, [4] amination reactions, [5] Mizoroki-Heck reactions, [6,7] hydroaminations, [8] hydrogenations, [9] additions, [10][11][12][13][14] N-heterocyclizations [15] and others. [16][17][18] Not only the employed phosphane substituents but also the size and electronic properties of the substituents at the 6-and 6Ј-position affect the catalytic activity of the derived transition metal complexes.…”

Section: Introductionmentioning

confidence: 99%

“…[3,19,20] In conjunction with our recent efforts to synthesize 2,2Ј,6,6Ј-tetraphosphanylbiphenyls [21] we gained access to valuable 2,2Ј,6,6Ј-tetrasubstituted biphenyls that allow the syntheses of new members of the above-mentioned class of diphosphanes. Comparisons between different spectra, especially 13 C{ 1 H}-DEPT90 data sets, allowed rough quantitation of compound ratios in the reaction mixtures. These diphos-Therefore, to find optimal conditions for complete formation of 10 (but at the same time avoiding degradation of the solvent and of dilithiated species 10) this reaction was monitored by sampling small quantities from a reaction mixture of 7 and 3 equiv.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 6,6′‐Bis(dimethylamino)‐ and 6,6′‐Dibromo‐Substituted 2,2′‐Diphosphanylbiphenyls and Their Palladium Complexes

et al. 2013

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New 6,6Ј-dibromo-and 6,6Ј-bis(dimethylamino)-substituted 2,2Ј-diphosphanylbiphenyl ligands 11-14 were prepared starting from 2,2Ј-dibromo-4,4Ј-dimethyl-6,6Ј-dinitro-1,1Ј-biphenyl (4). Depending on the phosphane groups [diphenylphosphanyl (11, 13) or diisopropylphosphanyl (12,14)] the palladium dichloride complexes show different coordination symmetry. Whereas the smaller diphenylphosphanyl groups lead to C 2 -symmetric complexes, the respective bis(diisopropyl)phosphanes 12 and 14 form C 1 -symmetric complexes that show fluxional behavior due to the restricted rotation of the isopropyl groups as well as the exchange of atom positions within the C 1 -symmetric conformer. All complexes have[a] TU Chemnitz, 4858 been tested as precatalysts in the Suzuki-Miyaura cross coupling reaction of 2-bromotoluene and phenylboronic acid. The activity of the catalytic system increases with the size of the diphosphanes and the donating ability of the ligand. In contrast to C 2 -symmetric palladium complex 15, platinum complex 19 was found to be C 1 -symmetric in the solid state despite the fact that both complexes have the small bis-(diphenylphosphanyl)-substituted diphosphane ligand 11 in common. NiBr 2 adduct 20 with a similar diphosphane 13 exists as a mixture of distorted square-planar and tetrahedral coordination sphere geometries in equilibrium with each other.Scheme 1. 1,1Ј-Biphenyl-2,2Ј-diyl-bridged diphosphanes discussed below and the numbering for relevant positions.phanes are of interest, as the large bromo substituents in the ortho positions lead to high activation barriers for the rotation around the central C-C bond. [22] Additionally, the dimethylamino groups can increase the electron density of the biphenyl system, [23] act as additional hemilabile donors [24] or form proton sponge systems. [25][26][27] Results and DiscussionLigands based on 2-phosphanyl-and 2,2Ј-diphosphanylbiphenyls are accessible by various methods employing electrophilic, [28] nucleophilic, [29] and radical chemistry [30] as well as transition-metal-catalyzed [31,32] reactions. A particularly effective method has been the treatment of a 2,2Ј-di-www.eurjic.org FULL PAPER lithiated biphenyl with a chlorophosphane. [28,33,34] Dilithiated biphenyl species are easily prepared by halogen/lithium exchange from the 2,2Ј-diiodo-/2,2Ј-dibromobiphenyls. We prepared diiodobiphenyl 6 and dibromobiphenyl 7 by the route depicted in Scheme 2. [35,36] The known diamine derivative 5 can be prepared from inexpensive and commercially available 4-methyl-2-nitroaniline (1). The methyl group in the 4-position blocks the C-4 atom from electrophilic attack by bromine in the first step to derivative 2; consequently, 2 is the only isolable regioisomer. [37] Moreover, the 4-methyl group improves the solubility of all compounds and simplifies workup procedures. The key step in the synthesis is an Ullmann [35,38] homo-coupling of iodo compound 3 to form the central C-C bond in 4. This reaction is highly selective and proceeds smoothly under relatively mild conditions in ...

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“…8 Bond distances and angles are similar to those reported for analogous cis-and trans-complexes, 8 including those containing chelating bisphosphines. 9,10 The B-O bond distances are typical for four coordinate borates containing catechol groups. There does not appear to be any significant interaction of the arylspiroborate anion and the rhodium center.…”

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Synthesis and Molecular Structure of [cis-Rh(PMePh2)2(NCCH3)2][BC28H40O4]

Vogels

Decken

Westcott

2012

X-ray Structure Analysis Online

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Arylspiroborates are a remarkable family of compounds containing two catecholato groups bound to a central boron atom that are usually nontoxic, inexpensive and thermally, chemically and electrochemically stable. 1 An attractive advantage of using these compounds is that they display relatively low toxicities towards mammals. Of particular interest to us is the ability of these species to bind to transition metals using different coordination sites. Metal complexes containing these ligands are active and selective catalyst precursors for a number of reactions, including the hydroboration of alkenes. 1 Our group has been investigating the synthesis and reactivity of novel arylspiroborates and we have recently prepared Tl[B(1,2-O2C6H2-3,5-di-tert-butyl)2]. 2 To examine whether this anion could coordinate to metal centers we added one equivalent of the thallium salt to an acetonitrile solution containing the in situ mixture of [Rh(m-Cl)(coe)2]2 and 4PMePh2 (coe = cyclooctene).We found that this reaction leads to a mixture of products including the cationic species [cis-Rh(PMePh2)2(NCCH3)2] + and anionic [BC28H40O4] -(1), shown in Fig. 1, where the bulky arylspiroborate ligand does not appear to bind to the metal centre. Yellow, parallelepiped crystals of 1 precipitated and were collected by suction filtration in 23% yield. The 13 P{ 1 H} NMR data showed a doublet at d 29.7 ppm with a coupling constant of JPRh = 171 Hz and the 11 B{ 1 H} NMR spectrum remains unchanged with a sharp singlet at d 13.9 ppm, suggesting that coordination of the arylspiroborate ester to the metal center did not occur. A single crystal X-ray diffraction study was performed to ascertain the configuration of ligands bound to the metal center.Single-crystal X-ray diffraction measurements were performed and a hemisphere of data was collected on a Bruker AXS P4/SMART 1000 diffractometer using w and q scans with a scan width of 0.3˚ and 10 s exposure times. The detector distance was 5 cm. The data were reduced (SAINT) 3 and corrected for absorption (SADABS). 4 The structure was solved by direct methods and refined by full-matrix least squares on The rhodium compound, [cis-Rh (PMePh2)2(NCCH3)2][BC28H40O4], was isolated and the molecular structure was determined by a single crystal X-ray diffraction study at 173 K. The compound crystallizes in a triclinic system, space group P1 and Z = 2 with cell parameters of a = 13.870 (3)

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Rhodium-Catalyzed Asymmetric Synthesis of Indanones: Development of a New “Axially Chiral” Bisphosphine Ligand

Cited by 75 publications

References 22 publications

Synthesis of 1-indanones with a broad range of biological activity

Synthesis of 1-indanones with a broad range of biological activity

Synthesis of 6,6′‐Bis(dimethylamino)‐ and 6,6′‐Dibromo‐Substituted 2,2′‐Diphosphanylbiphenyls and Their Palladium Complexes

Synthesis and Molecular Structure of [<i>cis</i>-Rh(PMePh<sub>2</sub>)<sub>2</sub>(NCCH<sub>3</sub>)<sub>2</sub>][BC<sub>28</sub>H<sub>40</sub>O<sub>4</sub>]

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