Asymmetric hydrogenation catalyzed by a chiral ferrocenylphosphine-rhodium complex

Hayashi, Tamio; Mise, Takaya; Mitachi, Seiko; Yamamoto, Keiji; Kumada, Makoto

doi:10.1016/s0040-4039(00)93770-5

Cited by 96 publications

(30 citation statements)

References 11 publications

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“…A S ( C~H~)~ for 7 As(CH3)~ for 8 P(C (CHdd2 for 9 cribed previously (13,15,19) but the other derivatives 7-9 are new. The analytical results, Table 1, and the nmr spectra, Table 2, confirm their formulation.…”

Section: Hydrogetlation Reactiotismentioning

confidence: 60%

“…Kumada and co-workers have found that rhodium(1) complexes of the amine and alcohol 18 (R = 16 17 DIOP ER2 = P(C6Hs)z OH or N(CH3),) are excellent hydrogenation catalysts (15,19,30,31). In view of the result that the closely related 6 gives complexes which are as effective, it was of interest to establish if the same would hold for the alcohol 11.…”

Section: Zn C Payne and D W Stephan Personal Communicationmentioning

confidence: 99%

“…The spectacular success in achieving nearly [,] (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15). One mechanism of the reaction, + 2 solvent based on studies of the commonl~ used substrates [3] …”

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confidence: 99%

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Asymmetric homogeneous hydrogenation of olefins catalyzed by alkylphosphine complexes of rhodium(I)

Cullen¹,

Woollins²

1982

Can. J. Chem.

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The cationic rhodium(I) complexes of the optically active ferrocenes, C5H5FeC5H3[CH(CH3)N(CH3)2][ER2]-1,2, catalyze the asymmetric hydrogenation of acetamidoacrylic acid derivatives, itaconic acid and styrene, when ER2 is P(C6H5)2 or P(C(CH3)3)2. The configuration of the product is reversed on substituting C6H5 for C(CH3)3 groups. The catalyst with the tert-butyl groups can afford higher optical yields and is faster overall. The rhodium(I) complexes of the arsenic derivatives ER2 = As(C6H5)2 or As(CH3)2 do not catalyze the hydrogenation reactions. The nmr spectrum of the arsenic complex (ER2 = As(C6H5)2) is temperature dependent which seems to be due to a process involving the making and breaking of the Rh—N bond. The unsuccessful use of the MEM group (β-methoxyethoxymethyl) to protect an alcohol function α to a ferrocene ring is described. The hydrogenation results are discussed in the light of models which are currently used to predict the results of rhodium(I) catalyzed reactions but which are inapplicable to this work.

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Section: Hydrogetlation Reactiotismentioning

confidence: 60%

Section: Zn C Payne and D W Stephan Personal Communicationmentioning

confidence: 99%

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Asymmetric homogeneous hydrogenation of olefins catalyzed by alkylphosphine complexes of rhodium(I)

Cullen¹,

Woollins²

1982

Can. J. Chem.

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“…One of the branches in ligand design was provided by Kumada and his introduction of the ferrocene backbone for BPPFA [99][100][101] (20a) and BPPOH [102] (20b). This development leads us to the next class of ligands -ferrocene-based.…”

Section: Diop 749mentioning

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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“…[3]. The initial reaction is carried out in strong acid solution (trichloroacetic acid/fluorosulfuric acid/acetic acid) and the overall yield of 1 is good (62%).…”

Section: Introductionmentioning

confidence: 99%

The synthesis of primary, secondary, and tertiary ferrocenylethylamines

Butler¹,

Cullen²

1983

Can. J. Chem.

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A simplified procedure for the preparation of α-N,N-dialkylaminoethylferrocenes R2NR′ (R = Me, C6H11, CHMe2; R′ = CH(CH3)C5H4FeC5H5) from the alcohol R′OH by treatment with HBr and R2NH is described. Use of ammonia results in the isolation of R′NH2, R′2NH (major product) and R′3N and use of the optically active amine d-(+)-H2NCH(CH3)C6H5 gives rise to diastereomers R′NHCH(CH3)C6H5 which are separable. When diphenylphosphine is substituted for an amine the oxide R′P(O)Ph2 is obtained in low yield. The secondary amine R′2NH reacts with n-butyllithium and chlorodiphenylphosphine to afford R′2NPPh2.

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Asymmetric hydrogenation catalyzed by a chiral ferrocenylphosphine-rhodium complex

Cited by 96 publications

References 11 publications

Asymmetric homogeneous hydrogenation of olefins catalyzed by alkylphosphine complexes of rhodium(I)

Asymmetric homogeneous hydrogenation of olefins catalyzed by alkylphosphine complexes of rhodium(I)

Enantioselective Alkene Hydrogenation: Introduction and Historic Overview

The synthesis of primary, secondary, and tertiary ferrocenylethylamines

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