Stereoselective substitution of α-aminoalkylferrocenes with diorganozincs. A fast synthesis of new chiral FERRIPHOS ligands for asymmetric catalysis

Lotz, Matthias; Ireland, Tania; Perea, Juan J. Almena; Knöchel, Paul

doi:10.1016/s0957-4166(99)00182-2

Cited by 41 publications

(24 citation statements)

References 8 publications

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“…The crude product was purified by column chromatography (CH 2 Cl 2 /Et 2 O 1:1 + 0.5% NEt 3 ) and afforded the amine 8a as an orange solid (960 mg, 2.4 mmol, 12%, dr 89:11) .54-7.50 (m, 2H), 7.38-7.33 (m, 2H), 7.28-7.22 (m, 1H), 4.36-4.34 (m, 1H), 4.24-4.23 (m, 1H), 4.10-4.08 (m, 1H), 3.91 (s, 1H), 3.57 (s, 1H), 2.02 (s, 6H); 13 C NMR (CDCl 3 ): d 144. 9, 128.7, 128.6, 127.7, 89.9, 81.5, 71.6, 71.3, 69.7, 69.1, 67.2, 66.0, 44.9; MS (EI, 70 eV) m=z (%): 399 (M þ +1, 14), 397 (M þ )1, 16), 356 (13), 355 (54), 354 (12), 353 (62), 309 (14), 275 (21), 274 (22), 273 (100), 217 (29), 216 (14), 215 (41), 203 (11), 202 (33), 154 (46), 153 (73), 134 (75), 121 (29), 56 (19), 43 (41); CHN calcd for C 19 H 20 BrFeN: C,57.32;H,5.06;N,3.52;Br,20.07. Observed: C,57.59;H,5.14;N,3.44;Br,19.44.…”

Section: (R)-[3-(nn-dimethylaminomentioning

confidence: 99%

“…Prepared according to the procedure described above from (S)-[3-(N,N-dimethylamino)propyl]ferrocene 12b (4.1 g, 15 mmol) with t-BuLi (14.1 mL, 23 mmol, 1.6 M solution in pentane, 1.5 equiv) and iodine (5.7 g, 23 mmol, 1.5 equiv) in Et 2 O (100 mL). The crude product was purified by column chromatography (n-pentane/Et 2 O 1:1 + 0.5% NEt 3 ) and afforded the amine 8c as an orange solid (3.7 g, 9.3 mmol, 62%, dr 93:7); mp 95-97°C; ½a D ¼ +26.2 (c 1.14, CHCl 3 ); IR 68.5,66.4,63.2,45.7,41.5,26.4,12.8;MS (EI,70 eV) m=z (%): 397 (M þ , 42), 369 (22), 368 (100), 353 (20), 312 (12), 226 (20), 184 (11), 121 (16) 9a. Prepared according to the procedure described above from (R)-[3-(N,N-dimethylamino)propyl]ferrocene 13a (1.3 g, 4.8 mmol) with t-BuLi (3.5 mL, 5.3 mmol, 1.5 M solution in pentane, 1.1 equiv) and iodine (1.4 g, 5.5 mmol, 1.15 equiv) in Et 2 O (100 mL).…”

Section: (R)-[3-(nn-dimethylaminomentioning

confidence: 99%

“…Prepared according to the procedure described above from (R)-[3-(N,N-dimethylamino)propyl]ferrocene 13a (1.3 g, 4.8 mmol) with t-BuLi (3.5 mL, 5.3 mmol, 1.5 M solution in pentane, 1.1 equiv) and iodine (1.4 g, 5.5 mmol, 1.15 equiv) in Et 2 O (100 mL). The crude product was purified by column chromatography (n-pentane/Et 2 O 1:1 + 0.5% NEt 3 ) and afforded the amine 9a as an orange solid (1.4 g, 3.4 1, 74.5, 72.1, 68.5, 66.4, 63.2, 45.7, 41.5, 26.4, 12.8 6, 74.7, 72.1, 68.6, 66.0, 58.0, 45.9, 41.6, 16.3; MS (EI, 70 eV) m=z (%): 384 (M þ +1, 19), 383 (M þ , 100), 369 (14), 368 (79), 340 (18), 339 (97), 338 (72), 337 (12), 336 (10), 312 (41), 213 (16), 212 (18), 211 (12), 208 (10), 184 (13), 155 (20), 154 (13), 153 (30), 152 (12), 128 (11), 121 (28), 72 (21), 56 (16); HRMS calcd for C 14 H 18 FeIN: 382.9833. Observed: 382.9846.…”

Section: (R)-[3-(nn-dimethylaminomentioning

confidence: 99%

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New efficient synthesis of Taniaphos ligands: application in ruthenium- and rhodium-catalyzed enantioselective hydrogenations

Tappe

Knöchel

2004

Tetrahedron: Asymmetry

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Section: (R)-[3-(nn-dimethylaminomentioning

confidence: 99%

Section: (R)-[3-(nn-dimethylaminomentioning

confidence: 99%

Section: (R)-[3-(nn-dimethylaminomentioning

confidence: 99%

See 1 more Smart Citation

New efficient synthesis of Taniaphos ligands: application in ruthenium- and rhodium-catalyzed enantioselective hydrogenations

Tappe

Knöchel

2004

Tetrahedron: Asymmetry

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“…The MandyPhos family of ligands (32) have been used to reduce enamides to aamino acids as well as an enol acetate to produce an a-hydroxy ester [134][135][136][137][138][139][140]. The substituents R and R 1 can be used for the fine-tuning of a specific substrate.…”

Section: Ferrocene Ligandsmentioning

confidence: 99%

Enantioselective Alkene Hydrogenation: Introduction and Historic Overview

Ager¹

2006

The Handbook of Homogeneous Hydrogenation

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23Enantioselective Alkene Hydrogenation: Introduction and Historic Overview Development of CAMP and DIPAMPDuring the late 1960s, Horner et al. [13] and Knowles and Sabacky [14] independently found that a chiral monodentate tertiary phosphine, in the presence of a rhodium complex, could provide enantioselective induction for a hydrogenation, although the amount of induction was small [15][16][17][18][19][20]. The chiral phosphine ligand replaced the triphenylphosphine in a Wilkinson-type catalyst [10,21,22]. At about this time, it was also found that [Rh(COD) 2 ] + or [Rh(NBD) 2 ] + could be used as catalyst precursors, without the need to perform ligand exchange reactions [23].Knowles found that the monophosphine CAMP (1a) could provide an ee-value of up to 88% for the reduction of dehydroamino acids. CAMP was an extension of PAMP (1b) that provides ee-values of 50-60% in analogous reactions [24]. At this time, Kagan showed that DIOP (2) (vide infra), where the stereogenic centers are not at phosphorus, could also provide enantioselective induction in an hydrogenation. DIOP also showed that a bisphosphine need not have the chirality at phosphorus, and that good stereoselectivity might result from a C 2 -symmetric ligand. Knowles then developed the C 2 -symmetric ligand DIPAMP (3) [22,25]. The use of Rh-DIPAMP for the synthesis of l-Dopa is well known and is still practiced today [12,22,27]. A number of variations of the DIPAMP structure were investigated for the synthesis of this important pharmaceutical, but the parent remains the best ligand in this class [22].

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“…He et al reported a diastereoselective substitution of αaminoalkylferrocenes with diethylzinc [69]. T h e configuration at the chiral center was retained in the products in the presence of 3-fold excess of diethylzinc or other organozinc reagents ( Table 28, ee% over 99%).…”

Section: Uses In Other Reactionsmentioning

confidence: 99%

Recently Developed Organometallic Complexes of Zn, Cu(Zn, Li), Fe, Ru and Less-used Ions. Use in Selective 1,2-or 1,4-Additions, Transfer Hydrogenations, Aldol Reactions and Diels-Alder Reactions

Zhu¹,

Jiang

Ren

et al. 2005

COS

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This review introduces the broad general topic of asymmetric organic synthetic reactions and reagents. Reagents containing both frequently used metallic ions, e.g. Zn ++ , Cu +(++) and Ru ++ , and rarely used ions, such as Ag + , employed in the construction of designed chiral centers, are updated here. Enantioselective 1,2-additions and 1,4-conjugate additions, transfer hydrogenations, and diasteroselective aldol reaction are discussed. The selectivities induced by chiral β-, δor γ-chiral amino alcohols, chiral diols, chiral binaphthyl derivatives, chiral P,N-containing auxiliaries, and other ligands used to prepare chiral metallic complexes, were compared in each reaction system. The use of two or more metallic ions with a single chiral ligand has now become a more popular strategy to catalyze chiral-center-controlled processes. For example, only diethylzinc was used in enantioselective additions to aldehydes in early studies. Recently, the combination of Et 2 Zn and Cu ++ in the selective additions has been used to achieve high ee% values and yields. Finally, quantum calculations have been used to obtain kinetic data to predict a reactions ee% values. For example, the calculated ∆G cal. values have a strong relationship with the obtained ∆G fit values which have the direct linkage with the ee% values. EntryActivator ee (%) at 0 °°°°C (config.) ee (%) at -45 °°°°C (config.)

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Stereoselective substitution of α-aminoalkylferrocenes with diorganozincs. A fast synthesis of new chiral FERRIPHOS ligands for asymmetric catalysis

Cited by 41 publications

References 8 publications

New efficient synthesis of Taniaphos ligands: application in ruthenium- and rhodium-catalyzed enantioselective hydrogenations

New efficient synthesis of Taniaphos ligands: application in ruthenium- and rhodium-catalyzed enantioselective hydrogenations

Enantioselective Alkene Hydrogenation: Introduction and Historic Overview

Recently Developed Organometallic Complexes of Zn, Cu(Zn, Li), Fe, Ru and Less-used Ions. Use in Selective 1,2-or 1,4-Additions, Transfer Hydrogenations, Aldol Reactions and Diels-Alder Reactions

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