Copper(I)-Catalyzed Asymmetric Desymmetrization: Synthesis of Five-Membered-Ring Compounds Containing All-Carbon Quaternary Stereocenters

Aikawa, Kohsuke; Okamoto, Tatsuya; Mikami, Kōichi

doi:10.1021/ja3032345

Cited by 77 publications

(38 citation statements)

References 45 publications

(55 reference statements)

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“…35 Hibino's group achieved the total synthesis through the microwave-assisted tandem Curtius rearrangement of 2-indolylbenzoic acid with DPPA followed by the electrocyclic ring closure of isocyanate 61 (Scheme 11). 36 Four simple synthetic approaches to neocryptolepine (cryptotackieine) (62) were developed. The one-pot formation of indolo [2,3-b]quinoline core 63 was achieved starting with the alkylation of 63 with acetate 64, followed by two reductive cyclizations to form an a-carboline system (Scheme 12).…”

Section: Non-tryptaminesmentioning

confidence: 99%

“…61 Diastereo-and enantioselective synthesis of the cyclopentene intermediate 118 for (+)-madindolines A (114) and B (115) was achieved using enantioselective desymmetrization of achiral cyclopentene 116 through Cu-catalyzed enantioselective methylation, followed by reaction of intermediary Zn-enolate with butylaldehyde to give 117, which was then converted to 118 (Scheme 31). 62 The rst biomimetic transformation of (+)-vincadifformine (119) to (À)-goniomitine (120) rac-Goniomitine (120) was synthesized using the Pd-catalyzed decarbonylative coupling of 121 with 122, followed by the one-pot oxidation/reduction/cyclization sequence (Scheme 33). 64 (À)-Mersicarpine (123), featuring a tetracyclic azepinoindole core, was synthesized through the DIBAH-promoted reductive ring expansion of oxime 124 to construct the azepinoindole core (Scheme 34).…”

Section: Non-tryptaminesmentioning

confidence: 99%

See 1 more Smart Citation

Simple indole alkaloids and those with a nonrearranged monoterpenoid unit

Ishikura,

Abe,

Choshi

et al. 2015

Nat. Prod. Rep.

213

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Section: Non-tryptaminesmentioning

confidence: 99%

Section: Non-tryptaminesmentioning

confidence: 99%

Simple indole alkaloids and those with a nonrearranged monoterpenoid unit

Ishikura,

Abe,

Choshi

et al. 2015

Nat. Prod. Rep.

213

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show abstract

“…9,10 This idea is highlighted by examples in ringclosing metathesis of trienes, 11 esterification of symmetric diols, 12 conjugate addition, 13,14 Ullmann coupling, 15 Suzuki coupling, 16 allylic substitution, 17 silylation of diols, 18 and oxidation. 19 Notably, C−C or C−N bonds are not formed or broken at the stereogenic center obtained through desymmetrization.…”

Section: ■ Introductionmentioning

confidence: 99%

Zirconium-Catalyzed Desymmetrization of Aminodialkenes and Aminodialkynes through Enantioselective Hydroamination

2015

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The catalytic addition of alkenes and amines (hydroamination) typically provides α-or β-amino stereocenters directly through C-N or C-H bond formation. Alternatively, desymmetrization reactions of symmetrical aminodialkenes or aminodialkynes provide access to stereogenic centers with the position controlled by the substrate's structure. In the present study of an enantioselective zirconium-catalyzed hydroamination, stereocenters resulting from C-N bond formation and desymmetrization of a prochiral quaternary center are independently controlled by the catalyst and reaction conditions. Using a single catalyst, the method provides selective access to either diastereomer of optically enriched five-, six-, and seven-membered cyclic amines from aminodialkenes and enantioselective synthesis of five-, six-, and seven-membered cyclic imines from aminodialkynes. Experiments on hydroamination of aminodialkenes testing the effects of the catalyst:substrate ratio, the absolute concentration of the catalyst, and the absolute initial concentration of the primary amine substrate show that the latter parameter strongly influences the stereoselectivity of the desymmetrization process, whereas the absolute configuration of the α-amino stereocenter generated by C-N bond formation is not affected by these parameters. Interestingly, isotopic substitution (H2NR vs D2NR) of the substrate enhances the stereoselectivity of the enantioselective and diastereoselective processes in aminodialkene cyclization and the peripheral stereocenter in aminodialkyne desymmetrization/cyclization. ABSTRACT: The catalytic addition of alkenes and amines (hydroamination) typically provides α-or β-amino stereocenters directly through C−N or C−H bond formation. Alternatively, desymmetrization reactions of symmetrical aminodialkenes or aminodialkynes provide access to stereogenic centers with the position controlled by the substrate's structure. In the present study of an enantioselective zirconium-catalyzed hydroamination, stereocenters resulting from C−N bond formation and desymmetrization of a prochiral quaternary center are independently controlled by the catalyst and reaction conditions. Using a single catalyst, the method provides selective access to either diastereomer of optically enriched five-, six-, and seven-membered cyclic amines from aminodialkenes and enantioselective synthesis of five-, six-, and seven-membered cyclic imines from aminodialkynes. Experiments on hydroamination of aminodialkenes testing the effects of the catalyst:substrate ratio, the absolute concentration of the catalyst, and the absolute initial concentration of the primary amine substrate show that the latter parameter strongly influences the stereoselectivity of the desymmetrization process, whereas the absolute configuration of the α-amino stereocenter generated by C−N bond formation is not affected by these parameters. Interestingly, isotopic substitution (H 2 NR vs D 2 NR) of the substrate enhances the stereoselectivity of the enantioselective and diastereoselecti...

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“…In a final example, a number of prochiral cyclopentene-1,3-diones have been desymmetrized by copper-catalyzed enantioselective additions of dialkylzinc or organoaluminum reagents. 92 The use of a phosphoramidite ligand such as 105 proved optimal in this method, as illustrated in the enantioselective synthesis of cyclopentene-1,3-dione 103 , a key step in the synthesis of (+)-madindoline B ( 104 ) (Fig. 10f).…”

Section: Desymmetrization Reactionsmentioning

confidence: 99%

Catalytic enantioselective synthesis of quaternary carbon stereocentres

Quasdorf

Overman

2014

Nature

850

341

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Preface Quaternary carbon stereocenters–carbon atoms to which four distinct carbon substituents are attached–are common features of molecules found in nature. However, prior to recent advances in chemical catalysis, there were few methods available for constructing single stereoisomers of this important structural motif. Here we discuss the many catalytic enantioselective reactions developed during the past decade for synthesizing organic molecules containing such carbon atoms. This progress now makes it possible to selectively incorporate quaternary stereocenters in many high-value organic molecules for use in medicine, agriculture, and other areas.

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Copper(I)-Catalyzed Asymmetric Desymmetrization: Synthesis of Five-Membered-Ring Compounds Containing All-Carbon Quaternary Stereocenters

Cited by 77 publications

References 45 publications

Simple indole alkaloids and those with a nonrearranged monoterpenoid unit

Simple indole alkaloids and those with a nonrearranged monoterpenoid unit

Zirconium-Catalyzed Desymmetrization of Aminodialkenes and Aminodialkynes through Enantioselective Hydroamination

Catalytic enantioselective synthesis of quaternary carbon stereocentres

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