Kinetic Resolution of <i>rac</i>-4,12-Dibromo[2.2]paracyclophane in a Palladium [2.2]PHANEPHOS Catalyzed Amination

Rossen, Kai; Pye, Philip J.; Maliakal, and Ashok J.; Volante, R. P.

doi:10.1021/jo971300a

Cited by 144 publications

(53 citation statements)

References 11 publications

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“…This Section contains a brief overview of the relevant literature citations for the various KR methodologies organized by functional group class: aldehydes (Horner-Emmons olefination, [60] hydroacylation [107] ); allylic alcohols (Sharpless epoxidation); [13,55] allylic carboxylates (palladium-catalyzed substitution); [36][37][38] allylic ethers (carbometallation); [58] alkenes (osmylations); [48,49] atropisomers; [35] azlactone cleavage; [14][15][16] 1,3-dioxolan-2,4-dione cleavage; [17] enones (hydrogenation, [22] cuprate addition [23e] ); Grignard reagents; [24a-f, 25] halides (palladium-catalyzed amine coupling); [113] ketones (aldol reaction, [23a] Baeyer-Villiger oxidation, [53] HornerEmmons olefination, [23b] enolization, [23c] organozinc addition, [23d] reduction, [23f, 50, 51] Noyori hydrogenation [18][19][20][21] ); lactones;…”

Section: Miscellaneous Functional Group Categoriesmentioning

confidence: 99%

Efficiency in Nonenzymatic Kinetic Resolution

2005

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The Walden memorial at the Technical University in Riga is pictured in the frontispiece to mark the recent centennial of the Walden inversion. This is a rare public monument to key events from the first era of exploration in stereocontrolled synthesis, and may be the only such monument to use the language of organic chemistry expressed at the molecular level. The reaction of racemic substrates with chiral nucleophiles is one of many methods currently known to achieve kinetic resolution, a phenomenon that ranks as the oldest and most general approach for the synthesis of highly enantioenriched substances. The first nonenzymatic kinetic resolutions as well as the original forms of the Walden inversion were studied in the 1890s. All of these investigations were conducted within the first generation following the demonstration that carbon is tetrahedral, and provided abundant evidence that the principles and importance of enantiocontrolled syntheses were understood. However, a reliable, rapid technique to quantify results and guide the optimization process was still lacking. Many decades passed before this problem was solved by the advent of HPLC and GLPC assays on chiral supports, which stimulated explosive growth in the synthesis of nonracemic substances by kinetic resolution. The Walden monument is accessible to passers-by for hands-on inspection as well as for contemplation and learning. In a similar way, kinetic resolution is experimentally accessible and can be thought-provoking at several levels. We follow the story of kinetic resolution from the early discoveries through fascinating historical milestones and conceptual developments, and close with a focus on modern techniques that maximize efficiency.

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Section: Miscellaneous Functional Group Categoriesmentioning

confidence: 99%

Efficiency in Nonenzymatic Kinetic Resolution

2005

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“…[14] A catalyst derived from palladium acetate and sulfonamide 81 promoted this reaction in an enantioselective manner. Benzene (78) was chosen as the substrate for the CÀH activation, and cyclic olefins were employed to ensure that achiral products were not formed (compare with VII in Scheme 3). With tert-butyl perbenzoate as the reoxidant, electron-deficient olefins 79 reacted at 100 8C to give arylated products 80 with up to 49 % ee and yields of 6 to 33 % yields [Eq.…”

Section: Reviewsmentioning

confidence: 99%

“…Another interesting aryl transfer reaction in which a primary amine serves as the aryl acceptor was recently disclosed by Rossen, Pye, et al [78] An enantioselective variant of the Hartwig/Buchwald coupling [79] was developed for the kinetic resolution of racemic 4,12-dibromo-[2.2]paracyclophane (90). Thus, when rac-90 was treated with benzylamine (91) in the presence of 2 mol % of a palladium catalyst containing (S)-[2.2]PHANEPHOS (95) [80] as the chiral ligand a product mixture consisting of monoaminated paracyclophane 92, a small amount of diamine 93, a dehalogenated derivative 94, and recovered starting material 90 was obtained [Eq.…”

Section: Asymmetric Arylations Of Aminesmentioning

confidence: 99%

Catalyzed Asymmetric Arylation Reactions

Bolm

Hildebrand

Muñiz

et al. 2001

Angew. Chem. Int. Ed.

340

124

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“…For example, PHANEPHOS has been shown to give good yields in the specific case of the resolution of 2,2 0 -dibromo [2,2]paracyclophane [110]. More extensive studies have not been reported.…”

Section: Amination Of Aryl Halidesmentioning

confidence: 99%

Palladium‐Catalyzed Amination of Aryl Halides and Sulfonates

Hartwig

2002

Modern Arene Chemistry

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The transition metal catalyzed synthesis of arylamines by the reaction of aryl halides or triflates with primary or secondary amines has become a valuable synthetic tool for many applications. This process forms monoalkyl or dialkyl anilines, mixed diarylamines or mixed triarylamines, as well as N-arylimines, carbamates, hydrazones, amides, and tosylamides. The mechanism of the process involves several new organometallic reactions. For example, the CaN bond is formed by reductive elimination of amine, and the metal amido complexes that undergo reductive elimination are formed in the catalytic cycle in some cases by NaH activation. Side products are formed by b-hydrogen elimination from amides, examples of which have recently been observed directly. An overview that covers the development of synthetic methods to form arylamines by this palladium-catalyzed chemistry is presented. In addition to the synthetic information, a description of the pertinent mechanistic data on the overall catalytic cycle, on each elementary reaction that comprises the catalytic cycle, and on competing side reactions is presented. The review covers manuscripts that appeared in press before June 1, 2001. This chapter is based on a review covering the literature up to September 1, 1999. However, roughly one-hundred papers on this topic have appeared since that time, requiring an updated review.

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Kinetic Resolution of rac-4,12-Dibromo[2.2]paracyclophane in a Palladium [2.2]PHANEPHOS Catalyzed Amination

Cited by 144 publications

References 11 publications

Efficiency in Nonenzymatic Kinetic Resolution

Efficiency in Nonenzymatic Kinetic Resolution

Catalyzed Asymmetric Arylation Reactions

Palladium‐Catalyzed Amination of Aryl Halides and Sulfonates

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