Phosphorus‐Bearing Axially Chiral Biaryls by Catalytic Asymmetric Cross‐Cyclotrimerization and a First Application in Asymmetric Hydrosilylation

Heller, Bárbara; Gutnov, Andrey; Fischer, Christine; Drexler, Hans‐Joachim; Spannenberg, Anke; Redkin, Dmitry; Sundermann, Corinna; Sundermann, Bernd

doi:10.1002/chem.200600826

Cited by 129 publications

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“…However, the solution 1 HN MR spectrum of the title complex shows two equivalent t-Bu groups, this being consistent with afast rotation of the P(O)(t-Bu) 2 substituent about the C4-P1 bond. The P-O bond length (1.49 Å) lies in the range expected for tertiary phosphine oxides [3][4][5]. …”

mentioning

confidence: 75%

Crystal structure of 5-di-tert-butylphosphinoyl-25,26,27,28-tetrabenzoyloxy- calix[4]arene – dichloromethane (1:1), C64H65O5P – CH2Cl2, C65H67Cl2O5P

Elaieb

Sémeril

Matt

et al. 2015

Zeitschrift Für Kristallographie - New Crystal Structures

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C 65 H 67 Cl 2 O 5 P, monoclinic, P2 1 /c (no. 14), a =16.118(1) Å, b =10.0843(7) Å, c =35.113(2) Å, b =104.009(3)°, V =5537.5 Å 3 , Z =4,R gt (F) =0.0930, wR ref (F 2 ) =0.1855, T =173 K. Source of materialTo as olution of 5-bromo-25,26,27,28-tetrabenzyloxycalix[4]arene (2.270 g, 2.63 mmol) in THF (100 mL) at -78°C was slowly added n-buthyllithium (5.26 mmol). After 0.5 h, the resulting organolithium compound was quenched with chloro(ditert-butyl)-phosphane (0.951 g, 5.26 mmol). The solution was allowed to reach room temperature and was stirred for an additional 16 h. Hydrogen peroxide (30% in water, 20 mL) was then added, and the mixture was stirred for 1h .T he aqueous phase was washed with CH 2 Cl 2 (2´20 mL). Thecombined organic phases were dried over Na 2 SO 4 and evaporated under reduced pressure. Experimental detailsThe cell parameters were determined using APEX2 software [6]. DiscussionThe asymmetric unit contains one molecule of the title compound. Thecalix[4]arene core adopts atypicalpinched cone conformation [1-3],w ith dihedral anglesb etween thep airs of opposite phenolic rings of -20.9°and 106.3°. The separation between the centroids of the distal phenoxy ring pairs are 4.82 Åand 7.72 Å, respectively. Note that the two distal phenoxy rings displaying the smaller interplane angle have their upper part, that is the carbon atomspara to the oxygen atomsO2and O4, slightly turned towards the calixarene axis (C18×××C46 :4 .36 Å; vs. C4×××C32 :9.98 Å). The P=O bond and the phenol ring to which it is attached arecoplanar. As aresult, oneofthe t-Bu groups is located above the upper cavity entrance, the other one is lying outside the cone. However, the solution 1 HN MR spectrum of the title complex shows two equivalent t-Bu groups, this being consistent with afast rotation of the P(O)(t-Bu) 2 substituent about the C4-P1 bond. The P-O bond length (1.49 Å) lies in the range expected for tertiary phosphine oxides [3][4][5].

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confidence: 75%

Crystal structure of 5-di-tert-butylphosphinoyl-25,26,27,28-tetrabenzoyloxy- calix[4]arene – dichloromethane (1:1), C64H65O5P – CH2Cl2, C65H67Cl2O5P

Elaieb

Sémeril

Matt

et al. 2015

Zeitschrift Für Kristallographie - New Crystal Structures

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“…757 The reaction culd also be potentially used for synthesis of chiral phosphorous-bearing 2-arylpyridine ligands. 758 …”

Section: Synthesis Of Six-membered Aromatic Heterocyclesmentioning

confidence: 99%

Transition Metal-Mediated Synthesis of Monocyclic Aromatic Heterocycles

et al. 2013

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“…[79] Biaryl 123 can be recrystallized to >99% ee , and after reduction, phosphine 124 can be used as an effective ligand for palladium-catalyzed asymmetric hydrosilylation of alkenes. Chiral helicenes can also be constructed with this [2+2+2] reaction using catalyst 118 , though in low (20% ee ) enantioselectivity.…”

Section: Cobalt Rhodium and Iridiummentioning

confidence: 99%

Indenylmetal Catalysis in Organic Synthesis

Trost

Ryan

2017

Angew Chem Int Ed

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Synthetic organic chemists have a long-standing appreciation for transition metal cyclopentadienyl complexes, of which many have been used as catalysts for organic transformations. Much less well known are the contributions of the benzo-fuzed relative of the cyclopentadienyl ligand, the indenyl ligand, whose unique properties have in many cases imparted differential reactivity in catalytic processes toward the synthesis of small molecules. In this review, we will present examples of indenylmetal complexes in catalysis and compare their reactivity to their cyclopentadienyl analogues, wherever possible.

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Phosphorus‐Bearing Axially Chiral Biaryls by Catalytic Asymmetric Cross‐Cyclotrimerization and a First Application in Asymmetric Hydrosilylation

Cited by 129 publications

References 59 publications

Crystal structure of 5-di-tert-butylphosphinoyl-25,26,27,28-tetrabenzoyloxy- calix[4]arene – dichloromethane (1:1), C64H65O5P – CH2Cl2, C65H67Cl2O5P

Crystal structure of 5-di-tert-butylphosphinoyl-25,26,27,28-tetrabenzoyloxy- calix[4]arene – dichloromethane (1:1), C64H65O5P – CH2Cl2, C65H67Cl2O5P

Transition Metal-Mediated Synthesis of Monocyclic Aromatic Heterocycles

Indenylmetal Catalysis in Organic Synthesis

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