Asymmetric synthesis catalyzed by chiral ferrocenylphosphine-transition metal complexes. 2. Nickel- and palladium-catalyzed asymmetric Grignard cross-coupling

Hayashi, Tamio; Konishi, Mitsuo; Fukushima, Moriyuki; Mise, Takaya; Kagotani, M.; Tajika, Masatoyo; Kumada, Makoto

doi:10.1021/ja00365a033

Cited by 250 publications

(74 citation statements)

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“…Kumada et al reported their ®ndings in comparing the impact of (S, R p )-PPFA with that of its diastereomer (R, R p )-PPFA and the analogue (S p )-FcPN with only planar chirality in a Nicatalyzed Grignard cross-coupling reaction [5]. They found that the planar chirality is a decisive factor for exerting control over enantiomer excess and absolute con®guration.…”

Section: Introductionmentioning

confidence: 99%

The application of ligands with planar chirality in asymmetric synthesis

Dai

Hou²,

Peng³

et al. 1999

Pure and Applied Chemistry

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Section: Introductionmentioning

confidence: 99%

The application of ligands with planar chirality in asymmetric synthesis

Dai

Hou²,

Peng³

et al. 1999

Pure and Applied Chemistry

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“…Optically active ferrocenyl derivatives are also used as a precursor for the chiral ferrocenylphosphine used in the preparation of scveral transition metal complexes which have been found to have catalytic activity in: ( i ) the asymmetric hydrogenation of olefins and ketones (3)(4)(5)(6); (ii) the asymmetric hydrosilation of olefins and ketones (7,8); (iii) the asymmetric isomerization of allylamines to enarnines (9); (iv) Grignard cross-coupling reactions (10). Several structures and absolute configurations of these derivatives and related complexes have been well characterized ( 2 , 4 , 11, 12).…”

Section: Introductionmentioning

confidence: 99%

Structure and absolute configuration of [1-(N,N-dimethylammonium)ethyl]ferrocene tartrate dihydrate

Luo¹,

Barton²,

Robertson³

1987

Can. J. Chem.

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. Can. J. Chem. 65, 2756Chem. 65, (1987. Crystals of [I-(N,N-dimethylammonium)ethyl]ferrocene tartrate dihydrate are triclinjc, space group P I , a = 7.235(1), b = I I .372(2), c = 12.724(3) A, a = 90.78(1), P = 102.75(1), y = 91.76(2)", V = 1020.3 at20 -t 2' C withZ = 2. Thestructure was solved by direct methods. The correct enantiomer was chosen based on full-matrix least-square refinements of each enantiomer. For the correct enantiomer, R = 0.031, R,,. = 0.035 for 11052 reflections with I 2 2u(I). Although the two crystallographically independent units of the complex in the structure are chemically equivalent, they are structurally different. The absolute configuration of the amino-substituted carbon aiom is (S), and that of the tartrate anion is (R,R). The mean ferrocenyl Fe-C bond lengths are 2.037 (2) [Traduit par la revue]

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“…(2)), then dynamic kinetic resolution could be achieved. Furthermore, equilibration of stereoisomers in dynamic kinetic resolutions is most often achieved by proton transfer, [3] addition-elimination reactions, [4] oxidation-reduction reactions, [5] or isomerization of configurationally labile carbanions, [6] whereas equilibration between stereoisomers containing all-carbon quaternary stereocenters can only be achieved through reversible CÀC bond-forming reactions, which have rarely been used so far in dynamic kinetic resolutions. Therefore, it may be possible to generate complex structures as single stereoisomers from a racemic starting material and an enantiopure reagent by developing cascade reactions with dynamic kinetic resolutions.…”

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confidence: 99%

Dynamic Kinetic Resolution during a Cascade Reaction on Substrates with Chiral All‐Carbon Quaternary Centers

Lalić

Sheehan

et al. 2005

Angew Chem Int Ed

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Dynamic kinetic resolution has become a useful method for the diastereoselective and enantioselective synthesis of organic compounds.[1] Dynamic kinetic resolution, presented in Equation (1) (Scheme 1), in its most common form results in greater than 50 % conversion of a mixture of stereoisomers into products enriched in one enantiomer or diastereoisomer. [2] Most dynamic kinetic resolutions require rapidly equilibrating enantiomeric starting materials that undergo a slower second step, in which the enantiomers react with enantiomerically enriched reagents at different rates (k 1R ¼ 6 k 1S ; Scheme 1, Eq. (1)). Conceptually, it is difficult to imagine how starting materials that are not directly susceptible to enantiomerization, such as molecules where the only chirality present is in all-carbon quaternary stereocenters, could take part in dynamic kinetic resolutions. However, if a molecule incapable of direct enantiomerization were to undergo a cascade reaction (a reaction comprising one or more intermediates) and if any one of the intermediates in the reaction was capable of epimerization or enantiomerization (I 1 , Scheme 1, Eq. (2)), then dynamic kinetic resolution could be achieved. Furthermore, equilibration of stereoisomers in dynamic kinetic resolutions is most often achieved by proton transfer, [3] addition-elimination reactions, [4] oxidation-reduction reactions, [5] or isomerization of configurationally labile carbanions, [6] whereas equilibration between stereoisomers containing all-carbon quaternary stereocenters can only be achieved through reversible CÀC bond-forming reactions, which have rarely been used so far in dynamic kinetic resolutions. Therefore, it may be possible to generate complex structures as single stereoisomers from a racemic starting material and an enantiopure reagent by developing cascade reactions with dynamic kinetic resolutions. Despite the potential of this concept, there are few examples of cascade reactions that incorporate dynamic kinetic resolution, especially ones involving the formation of multiple CÀC bonds. [7] Herein, we report on dyanmic-kinetic-resolution cascade reactions that occur with racemic starting materials that contain all-carbon quaternary stereocenters.During our synthesis of CP-263,114, we developed a diastereoselective cascade reaction comprising an alkylation, an anion-accelerated oxy-Cope rearrangement, and a transannular Dieckmann-like cyclization.[8] Using this latter reaction, we synthesized a wide range of complex polycyclic bridgehead enone compounds (Scheme 2).[9] The possible participation of intermediate 2 in a retro-aldol/aldol equilibrium and the consequences of this equilibrium on the transfer of stereochemistry from C2 of 1 to the product 4 was of particular interest to us (Scheme 3).[10]The occurance of the retro-aldol/aldol equilibration during the cascade reaction was tested with b-ketoester 5, which was prepared in 99 % ee by the enantioselective reduction of the corresponding racemate with the CoreyBakshi-Shibata (CBS) catalyst and...

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Asymmetric synthesis catalyzed by chiral ferrocenylphosphine-transition metal complexes. 2. Nickel- and palladium-catalyzed asymmetric Grignard cross-coupling

Cited by 250 publications

References 2 publications

The application of ligands with planar chirality in asymmetric synthesis

The application of ligands with planar chirality in asymmetric synthesis

Structure and absolute configuration of [1-(N,N-dimethylammonium)ethyl]ferrocene tartrate dihydrate

Dynamic Kinetic Resolution during a Cascade Reaction on Substrates with Chiral All‐Carbon Quaternary Centers

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