Diamidophosphites with isomeric carborane fragments: a comparison of catalytic activity in asymmetric Pd-catalyzed allylic substitution reactions

Lyubimov, S. E.; Davankov, V. A.; Gavrilov, K. N.; Grishina, Tatiana B.; Rastorguev, E. A.; Tyutyunov, A. A.; Verbitskaya, T. A.; Калинин, В. Н.; Hey‐Hawkins, Evamarie

doi:10.1016/j.tetlet.2010.01.084

Cited by 15 publications

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“…Enantioselectivities of up to 98% ee were obtained (see Scheme 3 ). With monodentate ligands L2 , 65 L4 , 60 and L5 ( 61 ) the same levels of enantioselectivity were also achieved with pyrrolidine and sodium para -toluene sulfinate as nucleophiles. Bauer’s group also studied other substrates using Pd– L8 as catalyst.…”

Section: Asymmetric Allylic Substitutionmentioning

confidence: 73%

“…Among the monodentate P-donor ligands developed since 2008 for Pd-catalyzed asymmetric allylic alkylation (AAA), diamidophosphites − and phosphoramidites − were found to provide higher enantioselectivities than their phosphite, , phosphinite, and phosphine − counterparts. Scheme collects the most representative families of monodentate P-donor ligands evaluated in the allylic alkylation of rac -1,3-diphenylallyl acetate as substrate with dimethyl malonate as nucleophile.…”

Section: Asymmetric Allylic Substitutionmentioning

confidence: 99%

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Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

362

202

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This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution and decarboxylative and oxidative allylic substitutions. For each reaction, the catalytic data, as well as examples of their application to the synthesis of more complex molecules, are collected. Sections in which we discuss key mechanistic aspects for high selectivity and a comparison with other metals (with advantages and disadvantages) are also included. For Pd-catalyzed asymmetric allylic substitution, the catalytic data are grouped according to the type of nucleophile employed. Because of the prominent position of the use of stabilized carbon nucleophiles and heteronucleophiles, many chiral ligands have been developed. To better compare the results, they are presented grouped by ligand types. Pd-catalyzed asymmetric decarboxylative reactions are mainly promoted by PHOX or Trost ligands, which justifies organizing this section in chronological order. For asymmetric oxidative allylic substitution the results are grouped according to the type of nucleophile used.

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Section: Asymmetric Allylic Substitutionmentioning

confidence: 73%

Section: Asymmetric Allylic Substitutionmentioning

confidence: 99%

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

362

202

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Carborane‐Substituted Bis(phosphino)hydrazines: Selective Formation of Six‐ and Twelve‐Membered P,N Heterocycles

2019

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Six-and twelve-membered heterocyclic carboranesubstituted bis(phosphino)hydrazines 1 and 2 were obtained selectively. Compound 1 was obtained as the major product in a 1:1 reaction, when the dilithiated o-carborane was added to 1,2-bis(dichlorophosphino)-1,2-diethylhydrazine, whereas the reverse addition led to 2 as the main product (2:2 reaction). Compound 1 was obtained only as the rac isomer, 2 as the [a] . FAB-MS, m/z: 693 (1 %, M + -C 2 H 5 ), 664 (2 %, M + -2C 2 H 5 ), 638 (3 %, M + -3C 2 H 5 ), 604 (M + -4C 2 H 5 ), 575 (1 %, M + -Cl -4C 2 H 5 ), 535 (1 %, M + -2Cl -4C 2 H 5 ), 463 (3 %, M + -4Cl -4C 2 H 5 ). rac-[{RhCl(η 4 -C 8 H 12 )} 2 {cyclo-1,2-(NEt) 2 -3,6-(PCl) 2 -4,5-(ortho-C 2 B 10 H 10 )-κP,κP′}] (3): [{Rh(μ-Cl)(cod)} 2 ] (0.30 g, 0.60 mmol) was dissolved in toluene (35 mL) and the solution added to a solution of 1 (0.22 g, 0.60 mmol) in toluene (35 mL). The solution was refluxed for 2 h and then concentrated to give an orange precipitate of 3. Single crystals of 3 were obtained from a concentrated toluene solution. Yield 0.47 g (90 %); m.p. 196°C, > 210°C (decomp.). 1 H NMR (CDCl 3 , -60°C): 5.78 and 5.97 (m, br, 8H, CH=CH), 3.85 and 4.22 (m, vbr, 4H, CH 2 of NEt), 3.96 and 3.67 (m, br, 8H, CH 2 of cod), 3.65-1.54 (m, vbr, 10H, C 2 B 10 H 10 ), 2.31 and 2.58 (m, br, 8H, CH 2 of cod), 1.47 (m, br, 6H, CH 3 ) ppm. 11 B{ 1 H} NMR (CDCl 3 , -60°C): -6.5 (m, br, 10B) ppm. 13 C NMR (CDCl 3 , -60°C): 114.5 (dd, 1 J CRh = 69.5 Hz, 2 J CP = 11.6 Hz, 1 J CH = 158.0 Hz, CH=CH), 76.4 (s, br, C cluster ), 48.6 (dt, 2 J PC = 23.2 Hz, 1 J CH = 141.8 Hz, CH 2 in NEt 2 ), 29.1 and 33.0 (dd, 2 J CRh = 84.0 Hz, 1 J CH = 130.7 Hz, CH 2 in cod), 16.6 (dq, 3 J PC = 11.2 Hz, 1 J CH = 128 Hz, CH 3 ) ppm. 31 P{ 1 H} NMR (CDCl 3 , -60°C): 114.6 (d, 1 J PRh = 225.6 Hz) ppm. IR (KBr, cm -1 ): , 964m, 937m, 903w, 870m, 822s, 791m, 762m, 744s, 673w, 642s, 623w, 571s, 521s, 487s, 474s. FAB-MS, m/z: 818 (10 %, M + -Cl), 710 (3 %, M + -Cl -C 8 H 12 ), 607 (40 %, M + -Cl -Rh -C 8 H 12 ), 572 (100 %, M + -2Cl -Rh -C 8 H 12 ).

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Chiral Rhodium(I) Complexes of 1,2‐Bis‐(chloroalkoxyphosphanyl)‐ and 1,2‐Bis‐(amidoalkoxyphosphanyl)‐1,2‐dicarba‐closo‐dodecaboranes(12)

et al. 2017

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1,2‐Bis(chloroalkoxyphosphanyl)‐1,2‐dicarba‐closo‐dodecaboranes(12) and 1,2‐bis(amido‐(‐)‐menthyloxyphosphanyl)‐1,2‐dicarba‐closo‐dodecaboranes(12) were synthesised by the reaction of dilithiated 1,2‐dicarba‐closo‐dodecaborane(12) with the corresponding dichloro‐ or chloroamidophosphite. For 1,2‐bis‐(chloro‐1‐adamantyloxyphosphanyl)‐1,2‐dicarba‐closo‐dodecaborane(12) epimerisation in solution was observed and the free activation enthalpy was determined experimentally and theoretically. An indirect determination of the meso configuration was obtained by formation of the corresponding molybdenum tetracarbonyl complex. Chlorido‐bridged dimeric chiral rhodium(I) complexes showing planar or folded Rh2Cl2 rings were prepared. Density functional calculations indicate that steric and packing factors play a much more significant role than electronic effects in influencing the bending of the rhodium complexes.

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Diamidophosphites with isomeric carborane fragments: a comparison of catalytic activity in asymmetric Pd-catalyzed allylic substitution reactions

Cited by 15 publications

References 14 publications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Carborane‐Substituted Bis(phosphino)hydrazines: Selective Formation of Six‐ and Twelve‐Membered P,N Heterocycles

Chiral Rhodium(I) Complexes of 1,2‐Bis‐(chloroalkoxyphosphanyl)‐ and 1,2‐Bis‐(amidoalkoxyphosphanyl)‐1,2‐dicarba‐closo‐dodecaboranes(12)

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