Asymmetric Synthesis of Isothiazoles through Cu Catalysis: Direct Catalytic Asymmetric Conjugate Addition of Allyl Cyanide to α,β‐Unsaturated Thioamides

Yanagida, Yasuo; Yazaki, Ryo; Kumagai, Naoya; Shibasaki, Masakatsu

doi:10.1002/ange.201102467

Cited by 35 publications

(4 citation statements)

References 38 publications

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“…Shibasaki et al 283 successfully developed the ACA of allyl cyanide to α,β-unsaturated thioamides promoted by complex L36a−[Cu(CH 3 CN) 4 ]BF 4 (Scheme 68), which provided the corresponding α,β-unsaturated nitriles with excellent enantiomeric purity in high yield. Moreover, various bioactive isothiazoles were successfully synthesized when the products were further treated with CuOTf/Li(OC 6 H 4 -p-OMe), in which CuOTf acted as a redox catalyst.…”

Section: Conjugate Addition Of Other Carbon Nucleophilesmentioning

confidence: 99%

Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles

2018

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The metal-catalyzed asymmetric conjugate addition (ACA) reaction has emerged as a general and powerful approach for the construction of optically active compounds and is among the most significant and useful reactions in synthetic organic chemistry. In recent years, great progress has been made in this area with the use of various chiral metal complexes based on different chiral ligands. This review provides comprehensive and critical information on the enantioselective 1,4-conjugate addition of nonorganometallic (soft) nucleophiles and their importance in synthetic applications. The literature is covered from the last 10 years, and a number of examples from before 2007 are included as background information. The review is divided into multiple parts according to the type of nucleophile involved in the reaction (such as C-, B-, O-, N-, S-, P-, and Si-centered nucleophiles) and metal catalyst systems used.

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Section: Conjugate Addition Of Other Carbon Nucleophilesmentioning

confidence: 99%

Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles

2018

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“…In an alternative approach, Kumagai, Shibasaki and co‐workers reported the synthesis of enantioenriched isothiazoles via Cu(I) catalysis through a cascade formation of C−C and N−S bonds (Scheme ) . The starting materials were prepared by a Cu‐catalyzed asymmetric conjugate addition of allyl cyanide to α,β‐unsaturated thioamides (not shown).…”

Section: Synthesis Of Isothiazolesmentioning

confidence: 99%

Recent Advances in the Synthesis and Reactivity of Isothiazoles

2019

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Isothiazoles represent an important class of five‐membered sulfur heterocycles that are widely utilized in medicinal chemistry and organic synthesis due to the unique properties of two electronegative heteroatoms in a 1,2‐relationship. However, in contrast to other 1,2‐azoles, the facile assembly of isothiazoles has always been considered a substantial challenge. In the last decade, major advances have taken place in the fields of synthesis and functionalization of isothiazoles that make them accessible to a wide range of interested chemists through unprecedented pathways. New condensation methods have emerged that address the challenges posed by unstable thiohydroxylamine. New metal‐catalyzed approaches have been reported that deliver densely decorated isothiazoles bearing various sensitive functional groups. New functionalization strategies have been developed through both cross‐coupling and direct C−H activation chemistry. Finally, the emergence of novel heterocyclic architectures based on isothiazole opens the door for future investigations of this versatile heterocyclic scaffold. This review covers the period from January 2004 to December 2018 and is intended as a sequel to the review on isoxazoles, which represent another class of synthetically‐important 1,2‐azoles (see Adv. Synth. Catal. 2015, 357, 2583–2614).

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“…Unfortunately, alkyl was not well tolerated at the γ-position as only moderate enantioselectivity was observed. Moreover, Shibasaki and Kumagai uncovered a catalytic asymmetric conjugate allylation of α,β-unsaturated thioamides with allyl cyanide under proton-transfer conditions 33 . In view of the above achievements, we are interested in developing a catalytic asymmetric conjugate 1,6-allylation with more general substrate structure and broader substrate scope.…”

Section: Introductionmentioning

confidence: 99%

“…Several research group made their contributions in the challenging catalytic asymmetric conjugate allylation (Fig. 1b) [25][26][27][28][29][30][31][32][33] . Snapper reported a Cu(II)-BOX-catalyzed asymmetric conjugate allylation of unsaturated cyclic β-ketoesters with allylsilane 25 .…”

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confidence: 99%

Copper(I)-catalyzed asymmetric 1,6-conjugate allylation

et al. 2020

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Catalytic asymmetric conjugate allylation of unsaturated carbonyl compounds is usually difficult to achieve, as 1,2-addition proceeds dominantly and high asymmetric induction is a challenging task. Herein, we disclose a copper(I)-NHC complex catalyzed asymmetric 1,6-conjugate allylation of 2,2-dimethyl-6-alkenyl-4H-1,3-dioxin-4-ones. The phenolic hydroxyl group in NHC ligands is found to be pivotal to obtain the desired products. Both aryl group and alkyl group at δ-position are well tolerated with the corresponding products generated in moderate to high yields and high enantioselectivity. Moreover, both 2-substituted and 3-substituted allylboronates serve as acceptable allylation reagents. At last, the synthetic utility of the products is demonstrated in several transformations by means of the versatile terminal olefin and dioxinone groups.

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Asymmetric Synthesis of Isothiazoles through Cu Catalysis: Direct Catalytic Asymmetric Conjugate Addition of Allyl Cyanide to α,β‐Unsaturated Thioamides

Cited by 35 publications

References 38 publications

Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles

Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles

Recent Advances in the Synthesis and Reactivity of Isothiazoles

Copper(I)-catalyzed asymmetric 1,6-conjugate allylation

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