Synthesis of Spiro Diphosphines and Their Application in Asymmetric Hydrogenation of Ketones

Xie, Jian‐Hua; Wang, Lixin; Fu, Yu; Zhu, Shuo‐Fei; Fan, Baomin; Duan, Haifeng; Zhou, Qi‐Lin

doi:10.1021/ja029907i

Cited by 292 publications

(99 citation statements)

References 36 publications

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“…The positioning of the substituents on the aromatic ring of acetophenone had significant effect on the outcome of reactions. The ortho-substituted acetophenones (2d-2f ) were converted to the desired alcohols with moderate enantioselectivities (70-77% ee, Table 2, entries 3-5), whereas meta-and para-substituted acetophenones (2g-2o) gave consistently high enantioselectivities (87-97% ee, Table 2, entries [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20].…”

Section: Resultsmentioning

confidence: 99%

A remarkably effective copper(II)-dipyridylphosphine catalyst system for the asymmetric hydrosilylation of ketones in air

Chan

2005

Proc. Natl. Acad. Sci. U.S.A.

105

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The combination of catalytic amounts of optically active dipyridylphosphine and CuF 2 along with hydride donor PhSiH3 generated in situ a remarkably reactive catalyst system (substrate-toligand molar ratio up to 100,000) for the highly enantioselective hydrosilylation of a broad spectrum of aryl alkyl ketones (up to 97% enantiomeric excess) in normal atmosphere and at mild conditions (ambient temperature to ؊20°C, compatible with traces of moisture) in the absence of base additives. Furthermore, a highly effective catalytic asymmetric hydrosilylation of unsymmetrical diarylketones using this catalyst system was also realized (up to 98% enantiomeric excess). The introduction of the dipyridylphosphine ligands in the air-accelerated and inexpensive metal-mediated asymmetric hydrosilylation of ketones makes the present system highly attractive and thus provides an excellent opportunity for practical applications.asymmetric catalysis C onsiderable efforts have been devoted to the development of efficient methods for the preparation of enantiomerically pure secondary alcohols because of the significance of these intermediates for the manufacture of pharmaceuticals and advanced materials. The catalytic asymmetric reduction of prochiral ketones as a direct route to enantiomeric alcohols is among the most attractive, and various strategies have been developed accordingly (1-5). Although intensive studies have been focused on the asymmetric hydrogenation that shows excellent enantioselectivities for a wide range of simple ketones (refs. 6 and 7 and references therein and refs. 8 -18), asymmetric hydrosilylation as a desirable alternative has also attracted much attention, owing to the mild reaction conditions used and technical simplicity (1d). Since the early reports three decades ago (19 -23), the asymmetric hydrosilylations of prochiral simple ketones mediated by catalysts of rhodium(I) (4, 24 -28) and ruthenium(II) (29, 30) as well as some less expensive metals such as titanium (31-34), zinc (35), tin (36), and copper(I) (37) have been extensively explored. However, most of these reactions were routinely conducted at a low substrate-to-ligand (S͞L) ratio (50 to 500). The high cost of catalyst and the low substrate-to-catalyst ratio rendered the previous hydrosilylation work unattractive commercially. More recently, a significant breakthrough in this area was achieved by , who developed a very effective catalyst system formed in situ from CuCl and nonracemic bidentate phosphines [e.g., (6,6Ј-dimethoxybiphenyl-2,2Ј-diyl)bis[di(3,5-dimethylphenyl)phosphine] (41, 42) or (4,4Ј-bi-1,3-benzodioxol)-5,5Ј-diylbis(di(3,5-di-tert-4-methoxyphenyl)phosphane) (43)] along with t-BuONa. This system allowed for highly active and enantioselective hydrosilylations of both aryl alkyl and heteroaromatic ketones in the presence of an inexpensive stoichiometric reductant polymethylhydrosiloxane (44) even at a S͞L molar ratio up to 100,000, which approached the levels achieved in related ruthenium-based asymmetric hydrogenations (ref. 6 and ...

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Section: Resultsmentioning

confidence: 99%

A remarkably effective copper(II)-dipyridylphosphine catalyst system for the asymmetric hydrosilylation of ketones in air

Chan

2005

Proc. Natl. Acad. Sci. U.S.A.

105

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“…2003 年, 周其林等 [15] 基于螺二氢茚骨架设计合成了手性螺环双膦配体 SDP (10) (图 2). 该手性螺环配体的双膦−钌−双胺催化剂(S a ,RR)-27a 在简单酮的不对称催化氢化反应中表现出了优异的催化活性 (TON 高达 100000)和对映选择性(高达＞99% ee) [15] (图 15, 式 23).…”

Section: 具有螺二氢茚骨架的手性螺环双磷配体unclassified

“…该手性螺环配体的双膦−钌−双胺催化剂(S a ,RR)-27a 在简单酮的不对称催化氢化反应中表现出了优异的催化活性 (TON 高达 100000)和对映选择性(高达＞99% ee) [15] (图 15, 式 23).…”

Section: 具有螺二氢茚骨架的手性螺环双磷配体unclassified

“…1997 年, 陈新滋、蒋耀忠等 [11] [14] 设计合成了首例具有螺二氢茚骨架的手性螺环单磷配体 SIPHOS (9), 并发现该配体对铑催化的脱氢氨基酸酯和烯酰胺等底物的不对称氢化反应具有优秀的手性诱导结果. 紧接着, 他们又设计合成了手性螺环双膦配体 SDP (10), 并在钌催化的简单酮的不对称氢化反应中获得了很高的对映选择性 (高达 99.6% ee)和催化活性(转化数, TON, 即底物与催化剂的物质的量之比, 达到 100000) [15] . 自此, 手性螺环配体才引起了化学家们的高度重视, 手性螺环配体也因此而得到了快速的发展.…”

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Magical Chiral Spiro Ligands

Xie¹,

Zhou²

2014

Acta Chim. Sinica

154

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Transition metal catalyzed asymmetric reaction is a hot issue and a frontier of the research in current organic chemistry. The design and synthesis of new type of efficient chiral ligands and chiral catalysts, esspecially those with novel skeleton is the focus of research in asymmetric catalysis. Since 1990's, chiral ligands based on spiro skeletons have received increasing attention and gradually developed into a new type of chiral ligands with distinctive characteristics. The skeletons of the chiral spiro ligands developed from spiro[4.4]nonane with three chiral stereocenters to spirobiindane and spiro[4.4]nonadiene with only one axial chirality, as well as other types of spiro skeletons. Nowadays, the library of chiral spiro ligands contains a wide range of chiral spiro ligands with different skeletons, including chiral spiro monophosphorus ligands, diphosphine ligands, phosphine-nitrogen ligands, dinitrogen ligands, and etc. Many of these chiral spiro ligands and related catalysts not only have shown high catalytic activity and high enantioselectivity for various asymmetric reactions such as asymmetric hydrogenations, asymmetric carbon-carbon bond forming reactions, and asymmetric carbon-heteroatom bond forming reactions, but also have made the enantiocontrol of many catalytic asymmetric reactions, which are difficult in obtaining high enantioselectivities, more easily and possible. The chiral spiro skeleton has become a 'privileged structure', and chiral spiro ligands and catalysts have been used in the syntheses of different type of chiral compounds including chiral natural products and chiral drugs. The emergence of chiral spiro ligands increased the dynamism of research on finding new chiral ligands and catalysts, and promoted asymmetric synthesis chemistry. Henceforth, the focus of study in chiral spiro ligands will continue to be the development of new chiral spiro ligands and catalysts with high activity and high enantioselectivity. At the same time, the applications of chiral spiro ligands in the new catalytic asymmetric reactions, and in the asymmetric synthesis of bioactive chiral compounds, chiral natural products and chiral drugs will become a new focus of research.

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“…Recently, we have developed a new type of axially chiral diphosphine ligands, SDP (1a ± d), based on the chiral 1,1'-spirobiindane scaffold [13] and found their Ru(II)-diphosphine-diamine complexes to be very effective in the ruthenium-catalyzed asymmetric hydrogenation of simple ketones (S/C up to 100,000 and ee up to 99.5%). This type of ligand has a rigid spiro backbone.…”

Section: Introductionmentioning

confidence: 99%

Application of SDP Ligands for Pd‐Catalyzed Allylic Alkylation

et al. 2004

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Chiral spiro diphosphines (SDP) are efficient ligands for the Pd-catalyzed asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate and related nucleophiles. The newly synthesized ligand DMM-SDP (1e) with 3,5-dimethyl-4-methoxy groups on the P-phenyl rings of the phosphine shows the highest enantioselectivity (up to 99.1% ee). Diethylzinc as a base is critical for obtaining high enantioselectivity in the allylic alkylation using b-dicarbonyl nucleophiles. The structure of catalyst [PdCl 2 ((S)-SDP)] was determined by single crystal X-ray diffraction. The SDP ligands create an effective asymmetric environment around the palladium, resulting in high enantioselectivities for the asymmetric allylic alkylation reaction

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Synthesis of Spiro Diphosphines and Their Application in Asymmetric Hydrogenation of Ketones

Cited by 292 publications

References 36 publications

A remarkably effective copper(II)-dipyridylphosphine catalyst system for the asymmetric hydrosilylation of ketones in air

A remarkably effective copper(II)-dipyridylphosphine catalyst system for the asymmetric hydrosilylation of ketones in air

Magical Chiral Spiro Ligands

Application of SDP Ligands for Pd‐Catalyzed Allylic Alkylation

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