Chiral N-(tert-butyl)-N-methylaniline type ligands: synthesis and application to palladium-catalyzed asymmetric allylic alkylation

Mino, Takashi; Asakawa, Minato; Shima, Yamato; Yamada, Haruka; Yagishita, Fumitoshi; Sakamoto, Masami

doi:10.1016/j.tet.2015.01.027

Cited by 20 publications

(4 citation statements)

References 28 publications

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“…270 Mino's group described another example of backbone control with the atropoisomeric 1-diphenylphosphino-2-amino ligand L83 inducing ee values of up to 95% in the allylic alkylation of rac-1,3-diphenylallyl acetate (Scheme 77). 268,282 Later on, Miller's group extended Mino's design to amides (ligand L84; ee values up to 92%, Scheme 77). 280 A second strategy to favor stereoselective coordination of the N-group relies on introducing chiral substituents at the Ngroup.…”

Section: T H Imentioning

confidence: 99%

“…The quest for more stable and inexpensive ligands spurred the interest for bidentate heterodonor P,N(sp 3 )-ligands. In most examples either amines − or amides − were used as N-donor groups and most studies focused on reactions of the benchmark linear substrate with dimethyl malonate as nucleophile (see Scheme ). The low selectivity of this class of ligand has been attributed to the low stereoselective coordination of the N-sp 3 group, which leads to the formation of diastereoisomeric mixtures of catalytic species.…”

Section: Asymmetric Allylic Substitutionmentioning

confidence: 99%

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Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

369

202

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This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution and decarboxylative and oxidative allylic substitutions. For each reaction, the catalytic data, as well as examples of their application to the synthesis of more complex molecules, are collected. Sections in which we discuss key mechanistic aspects for high selectivity and a comparison with other metals (with advantages and disadvantages) are also included. For Pd-catalyzed asymmetric allylic substitution, the catalytic data are grouped according to the type of nucleophile employed. Because of the prominent position of the use of stabilized carbon nucleophiles and heteronucleophiles, many chiral ligands have been developed. To better compare the results, they are presented grouped by ligand types. Pd-catalyzed asymmetric decarboxylative reactions are mainly promoted by PHOX or Trost ligands, which justifies organizing this section in chronological order. For asymmetric oxidative allylic substitution the results are grouped according to the type of nucleophile used.

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Section: T H Imentioning

confidence: 99%

Section: Asymmetric Allylic Substitutionmentioning

confidence: 99%

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

369

202

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“…[3] The potential of N À C axially chiral compounds also encompasses the fields of agrochemistry (e.g. the herbicide metolachlore), [4] asymmetric catalysis through the development of new chiral ligands, [5] and material science (Figure 1). [6] However, the enantioselective synthesis of NÀC axially chiral molecules remains strongly underdeveloped (Figure 2).…”

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confidence: 99%

Enantioselective Synthesis of N–C Axially Chiral Compounds by Cu‐Catalyzed Atroposelective Aryl Amination

et al. 2020

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N−C axially chiral compounds have emerged recently as appealing motifs for drug design. However, the enantioselective synthesis of such molecules is still poorly developed and surprisingly no metal‐catalyzed atroposelective N‐arylations have been described. Herein, we disclose an unprecedented Cu‐catalyzed atroposelective N−C coupling that proceeds at room temperature. Such mild reaction conditions, which are a crucial parameter for atropostability of the newly generated products, are operative thanks to the use of hypervalent iodine reagents as a highly reactive coupling partners. A large panel of the N−C axially chiral compounds was afforded with very high enantioselectivity (up to >99 % ee) and good yields (up to 76 %). Post‐modifications of thus accessed atropisomeric compounds allows further expansion of the diversity of these appealing compounds.

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“…8 On the other hand, we reported the synthesis of P/N-type ligands with C(aryl)-N(amine) bond axial chirality, such as chiral N-aryl indoline-type aminophosphine L1, 9 chiral N-aryl indole-type aminophosphine L2, 10 and acyclic chiral aminophosphines L3 11 and L4. 12 We also reported that aminophosphine L2 was an effective ligand for the palladium-catalyzed asymmetric allylic alkylation of indoles. 13 We are interested in chiral phosphine-internal olefin hybrid type ligands 14,15 with the C(aryl)-N(amine) bond axial chirality of aniline derivatives.…”

Section: Introductionmentioning

confidence: 94%

Chiral N-1-adamantyl-N-trans-cinnamylaniline type ligands: synthesis and application to palladium-catalyzed asymmetric allylic alkylation of indoles

et al. 2016

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Chiral N-(tert-butyl)-N-methylaniline type ligands: synthesis and application to palladium-catalyzed asymmetric allylic alkylation

Cited by 20 publications

References 28 publications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Enantioselective Synthesis of N–C Axially Chiral Compounds by Cu‐Catalyzed Atroposelective Aryl Amination

Chiral N-1-adamantyl-N-trans-cinnamylaniline type ligands: synthesis and application to palladium-catalyzed asymmetric allylic alkylation of indoles

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