P-Chirogenic Diaminophosphine Oxide:  A New Class of Chiral Phosphorus Ligands for Asymmetric Catalysis

Nemoto, Tetsuhiro; Matsumoto, Takayoshi; Masuda, Takamasa; Hitomi, Tsukasa; Hatano, Keiichiro; Hamada, Y.

doi:10.1021/ja031792a

Cited by 130 publications

(47 citation statements)

References 21 publications

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“…After concentration in vacuo, the obtained residue was purified by flash column chromatography (SiO 2 , hexane/AcOEtϭ4/1 to 1/1) to give (S,R P )-9a (213.1 mg, 27% yield) and (S,S P )-9b (431. 8 2 (1.1 mg, 0.003 mmol), (S,S P )-9b (3.3 mg, 0.006 mmol) in CH 2 Cl 2 (1 ml) at room temperature was added BSA (222 ml, 0.90 mmol). After being stirred for 10 min at the same temperature, a CH 2 Cl 2 solution of 11 (76.0 mg, 0.30 mmol in 0.5 ml of CH 2 Cl 2 ) and dimethyl malonate (103 ml, 0.90 mmol) were added successively to the reaction at 4°C.…”

Section: Compound (Sr P )-9a and (Ss P )-9bmentioning

confidence: 99%

“…These preligands have been successfully applied to Pd-and Ir-catalyzed asymmetric allylic substitution reactions. [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] Detailed investigations into the reaction mechanism using a Pd-catalyzed asymmetric allylic alkylation of 1,3-diphenylallyl acetate with dimethyl malonate revealed that complex 3 [Pd-2 (1 : 2) complex] was the active catalyst. 9) With this result in hand, we became interested in the development of bidentate P-chiral diaminophosphine oxide preligands with an achiral diphenylphosphine moiety as the second coordinating group.…”

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confidence: 99%

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Synthesis of Novel Bidentate P-Chiral Diaminophosphine Oxide Preligands: Application to Pd-Catalyzed Asymmetric Allylic Substitution Reactions

Harada

Nemoto

Jin

et al. 2011

CHEMICAL & PHARMACEUTICAL BULLETIN

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We developed a novel (S)-L-phenylalanine derived-bidentate chiral diaminophosphine oxide (DIAPHOX) preligand (S,S P )-9b, which was successfully applied to Pd-catalyzed asymmetric allylic alkylation and amination. Using the Pd-(S,S P )-9b catalyst system, asymmetric allylic alkylation and amination proceeded very smoothly, affording the corresponding products in excellent yield with high enantiomeric excess. It is noteworthy that both enantiomers were accessible with high enantiomeric purity using the structurally related DIAPHOX preligands (S,S P )-9b and a monodentate chiral diaminophosphine oxide preligand (S,R P )-10a, both of which can be prepared from a single chiral source, (S)-L-phenylalanine.Key word chiral diaminophosphine oxide; asymmetric allylic substitution; palladium; asymmetric catalysis; preligand Chem. Pharm. Bull. 59(3) 412-415 (2011)

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Section: Compound (Sr P )-9a and (Ss P )-9bmentioning

confidence: 99%

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confidence: 99%

Synthesis of Novel Bidentate P-Chiral Diaminophosphine Oxide Preligands: Application to Pd-Catalyzed Asymmetric Allylic Substitution Reactions

Harada

Nemoto

Jin

et al. 2011

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…30). 29) Catalytic enantioselective construction of a quaternary carbon center is a formidable challenge in organic synthesis. [32][33][34][35] Pd-catalyzed asymmetric allylic substitution using prochiral nucleophiles is one of the most straightforward approaches toward this end.…”

Section: Pd-catalyzedmentioning

confidence: 99%

“…28) 1. Design and Synthesis of P-Chirogenic Diaminophosphine Oxides: DIAPHOXs 29) Cyclic diaminophosphine oxides with a stereogenic center on the phosphorus atom can be prepared from chiral (or achiral) asymmetric diamines. Separation of the diastereomeric (or enantiomeric) mixture, however, is necessary to obtain optically pure P-chirogenic diaminophosphine oxide.…”

Section: Introductionmentioning

confidence: 99%

Transition Metal-Catalyzed Asymmetric Reactions Using P-Chirogenic Diaminophosphine Oxides: DIAPHOXs

Nemoto

2008

CHEMICAL & PHARMACEUTICAL BULLETIN

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This review describes the development of a new class of chiral phosphorus ligands: amino acid-derived Pchirogenic diaminophosphine oxides, DIAPHOXs, and their application to several transition metal-catalyzed asymmetric allylic substitution reactions. Pd-catalyzed asymmetric allylic alkylation with cyclic b b-keto esters as prochiral nucleophiles was initially examined using P-chirogenic diaminophosphine oxide 1a, resulting in highly enantioselective construction of quaternary stereocenters. Mechanistic investigations revealed that 1a is activated by N,O-bis(trimethylsilyl)acetamide-induced tautomerization to afford a trivalent diamidophosphite species 13, which functions as the actual ligand. Pd-catalyzed asymmetric allylic substitutions of both acyclic and cyclic substrates were also examined using various nucleophiles such as malonate derivatives, nitromethane, aliphatic amines, and aromatic amines, providing a variety of chiral compounds with good to excellent enantioselectivity. In addition, Ir-catalyzed asymmetric allylic amination and alkylation of terminal allylic carbonates were examined using structurally optimized P-chirogenic diaminophosphine oxides, and the corresponding branched products were obtained in a highly regio-and enantioselective manner. Furthermore, the developed catalytic asymmetric process was successfully applied to the catalytic enantioselective synthesis of biologically active compounds, (R)-preclamol, (R)-baclofen hydrochloride, and (؊)-paroxetine.

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“…From a drug discovery perspective, this method provides access to useful building blocks with a single quaternary stereocenter. [53,54] …”

Section: Introductionmentioning

confidence: 99%

Application of Hydroxyporphyrins-based Phosphite-type Ligands to Asymmetric Pd-Catalyzed Allylic Substitution Reactions

Konstantin¹,

Sergey²,

Marina³

et al. 2015

MHC

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P-Chirogenic Diaminophosphine Oxide: A New Class of Chiral Phosphorus Ligands for Asymmetric Catalysis

Cited by 130 publications

References 21 publications

Synthesis of Novel Bidentate P-Chiral Diaminophosphine Oxide Preligands: Application to Pd-Catalyzed Asymmetric Allylic Substitution Reactions

Synthesis of Novel Bidentate P-Chiral Diaminophosphine Oxide Preligands: Application to Pd-Catalyzed Asymmetric Allylic Substitution Reactions

Transition Metal-Catalyzed Asymmetric Reactions Using P-Chirogenic Diaminophosphine Oxides: DIAPHOXs

Application of Hydroxyporphyrins-based Phosphite-type Ligands to Asymmetric Pd-Catalyzed Allylic Substitution Reactions

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