Preparation of new chiral pyrrolidinebisphosphines as highly effective ligands for catalytic asymmetric synthesis of R-(−)-pantolactone

Takahashi, Hisashi; Hattori, Masaaki; Chiba, Mitsuo; Morimoto, Toshiaki; Achiwa, Kazuo

doi:10.1016/s0040-4039(00)84983-7

Cited by 72 publications

(16 citation statements)

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“…22) The absolute configurations of (R)-and (S)-BICHEP bearing a similar structure to 8b had been also determined by comparison of their CD spectra with those of (R)-and (S)-BIPHEMP. 23) Catalytic asymmetric hydrogenation of functionalized olefins such as itaconic acid (9), a-piperonylidenesuccinic acid monomethyl ester (11), and (Z)-a-acetamidocinnamic acid (13) was carried out by using cationic rhodium complexes of (R)-8a-c. The results are summarized in Tables 1 and 2.…”

Section: Resultsmentioning

confidence: 99%

“…complexes as catalyst. We previously proposed a novel idea, "respective control concept" for designing new chiral ligands, 7-10) and developed efficient diphosphine ligands such as (2S-cis)-4-(dicyclohexylphosphino)-2-[(diphenylphosphino)methyl]-1-pyrrolidinecarboxylic acid 1,1-dimethylethyl ester (BCPM) and its analogs, 8,[11][12][13] (4R-trans)-[(2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene)]bis[bis(4-methoxy-3,5-dimethylphenyl)phosphine] (MOD-DIOP) and its analogs, [14][15][16][17] etc. (Fig.…”

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Preparation of Axially Chiral Biphenyl Diphosphine Ligands and Their Application in Asymmetric Hydrogenation

et al. 2004

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Development of efficient methods for catalytic enantioselective synthesis has been an important subject for the practical synthesis of optically active organic compounds.1) Numerous methods of enantioselective synthesis employing various catalysts such as transition metal complexes coordinated with many types of chiral ligands have been reported for more than three decades. [1][2][3][4][5][6] For the development of efficient chiral catalysts, creation of new types of ligands is a most significant strategy. Among various types of chiral ligands, diphosphines are the most effective and are widely applicable in the catalytic asymmetric hydrogenation of prochiral compounds such as olefins, ketones, and imines using transition metal (rhodium, ruthenium, iridium, etc.) complexes as catalyst. We previously proposed a novel idea, "respective control concept" for designing new chiral ligands, 7-10) and developed efficient diphosphine ligands such as (2S-cis)-4-(dicyclohexylphosphino)-2-[(diphenylphosphino)methyl]-1-pyrrolidinecarboxylic acid 1,1-dimethylethyl ester (BCPM) and its analogs, 8,[11][12][13] (4R-trans)-[(2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene)]bis[bis(4-methoxy-3,5-dimethylphenyl)phosphine] (MOD-DIOP) and its analogs, [14][15][16][17] etc. (Fig. 1) for rhodium-catalyzed asymmetric hydrogenation of some prochiral ketones (ketopantolactone, a-and bamino ketones, etc.), and olefins (itaconic acid and its derivatives, N-acyldehydroamino acids, etc.). Furthermore, we revealed that phosphines bearing electron-donating groups such as cyclohexyl groups, p-(dimethylamino)phenyl groups, and p-methoxy-m,mЈ-dimethylphenyl groups enhance not only the catalytic activity but also the enantioselectivity in the rhodium-catalyzed hydrogenations. The p-methoxym,mЈ-dimethylphenyl (abbreviated to MOD) group was found to be a useful component for developing efficient ligands on the basis of its steric effect (m-Me) as well as its electronic effect (p-MeO, m-Me).15) We also reported in preliminary communications the design and preparation of axially chiral diphosphines, [18][19][20][21] which were found to be very efficient ligands for ruthenium-catalyzed asymmetric hydrogenation of a b-keto ester or rhodium-catalyzed asymmetric hydrogenation of an a-amino ketone. In this article we describe in detail the synthesis of optically pure 3,3Ј-dimethoxy-2,2Ј,4,4Ј-tetramethyl-1,1Ј-biphenyls 8a-c bearing one or two 6,(6Ј)-dicyclohexylphosphino group(s) and/or 6,(6Ј)-diphenylphosphino group(s), and an application to rhodium-catalyzed asymmetric hydrogenation. Results and DiscussionThe synthetic route of axially dissymmetric biphenyldiphosphine ligands 8a-c bearing one or two dicyclohexylphosphino group(s) and/or one or two diphenylphosphino group(s) is described in Chart 1 (8a-c were abbreviated to BIMOP, Cy-BIMOP, and MOC-BIMOP, respectively). Iodination of 2,6-dimethylnitrobenzene (1) was carried out selectively at the 3-position by heating with iodine at 90°C for 4 d in the presence of periodic acid in acetic acid containing d...

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Preparation of Axially Chiral Biphenyl Diphosphine Ligands and Their Application in Asymmetric Hydrogenation

et al. 2004

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“…1 During the past few decades, the enantiomerically pure amino alcohols, especially 1,2-amino alcohols, have also been employed as chiral auxiliaries and resolving agents for acids and as chiral ligands in catalysts for applications in catalytic asymmetric synthesis. 2 Chiral 1,2-amino alcohols are generally prepared from naturally occurring amino acids, 3 reduction of a-amino carbonyl compounds, 4 a-hydroxy carbonyl compounds, 5 from the stereo-, regio-and enantioselective ring opening of epoxides, 6 amino hydroxylations of olefins 7 and asymmetric hydroboration of enamines. 8 These amino alcohols can also be obtained in enantiomerically pure form via resolution of racemic amino alcohols, especially for obtaining both enantiomers in enantiomerically pure forms, but only a few methods are available.…”

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New, Convenient Methods of Synthesis and Resolution of 1,2-Amino Alcohols

Periasamy¹,

Sivakumar²,

Reddy³

2003

Synthesis

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“…如 Achiwa 等 [50] 运用酒石酸衍生物出发合成了配合物 46 用于烯烃的氢化, 对映选择性高达 95%. 由张兆国等 [51] [59,60] , 在用于烯烃的氢化反应中 ee 值可以达到 65%; 通过对磷、氮上取代基的改变合成了类似物 51～53 [61] , 在催化酮的氢化还原过程中 ee 值分别达到了 66.3%, 72.8%, 92.0%; 类似的含有氮杂环的配体 AMPP 54 [37] 也已经被合成出来, 被用在 α-官能团的酮的氢化还原中, 且取得了 ee 值达到 90%以上的立体选择性; Rajanbabu 等 [62] 合成了系列配体 55, 用于催化氢化反应中, 得到产物的 ee 值均可以达到 91%以上; 同样由木糖得到了配体 56 [63] , 催化反应的 ee 值达到了 90%等.…”

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