Catalytic Amide-Base System of TMAF and N(TMS)                         3                          for Deprotonative Coupling of Benzylic C(sp                         3                         )-H Bonds with Carbonyls

Masanori Shigeno; Kunihito Nakaji; Kanako Nozawa-Kumada; Yoshinori Kondo

doi:10.1021/acs.orglett.9b00550

Catalytic Amide-Base System of TMAF and N(TMS) ₃ for Deprotonative Coupling of Benzylic C(sp ³ )-H Bonds with Carbonyls

Masanori Shigeno, Kunihito Nakaji, Kanako Nozawa-Kumada, Yoshinori Kondo

PHA - Molecular Pharmaceutical Science

Tohoku University

Research output: Contribution to journal › Article › peer-review

24 Citations (Scopus)

Abstract

This paper describes that an amide-base generated in situ from tetramethylammonium fluoride (TMAF) and N(TMS) ₃ catalyzes the deprotonative coupling of benzylic C(sp ³ )-H bonds with carbonyls to form stilbenes. A variety of methylheteroarenes (2-methylbenzothiophene, 2-methylbenzofuran, and 2-, 3-, or 4-methylpyridines) are used as nucleophiles. Application to enamine synthesis using DMF as an electrophile is also shown. The present system is effective for toluenes (4-phenyl-, 4-bromo-, 2-bromo-, and 4-chlorotoluenes) having low reactivity.

Original language	English
Pages (from-to)	2588-2592
Number of pages	5
Journal	Organic Letters
Volume	21
Issue number	8
DOIs	https://doi.org/10.1021/acs.orglett.9b00550
Publication status	Published - 2019 Apr 19

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Shigeno, M., Nakaji, K., Nozawa-Kumada, K., & Kondo, Y. (2019). Catalytic Amide-Base System of TMAF and N(TMS) ₃ for Deprotonative Coupling of Benzylic C(sp ³ )-H Bonds with Carbonyls Organic Letters, 21(8), 2588-2592. https://doi.org/10.1021/acs.orglett.9b00550

Shigeno, Masanori ; Nakaji, Kunihito ; Nozawa-Kumada, Kanako et al. / Catalytic Amide-Base System of TMAF and N(TMS) ₃ for Deprotonative Coupling of Benzylic C(sp ³ )-H Bonds with Carbonyls In: Organic Letters. 2019 ; Vol. 21, No. 8. pp. 2588-2592.

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title = " Catalytic Amide-Base System of TMAF and N(TMS) 3 for Deprotonative Coupling of Benzylic C(sp 3 )-H Bonds with Carbonyls ",

abstract = " This paper describes that an amide-base generated in situ from tetramethylammonium fluoride (TMAF) and N(TMS) 3 catalyzes the deprotonative coupling of benzylic C(sp 3 )-H bonds with carbonyls to form stilbenes. A variety of methylheteroarenes (2-methylbenzothiophene, 2-methylbenzofuran, and 2-, 3-, or 4-methylpyridines) are used as nucleophiles. Application to enamine synthesis using DMF as an electrophile is also shown. The present system is effective for toluenes (4-phenyl-, 4-bromo-, 2-bromo-, and 4-chlorotoluenes) having low reactivity.",

author = "Masanori Shigeno and Kunihito Nakaji and Kanako Nozawa-Kumada and Yoshinori Kondo",

note = "Funding Information: This work was financially supported by JSPS KAKENHI Grant No. 16H00997 in Precisely Designed Catalysts with Customized Scaffolding (Y.K.), JSPS KAKENHI Grant No. 17K15419 (M.S.), Grand for Basic Science Research Projects from The Sumitomo Foundation (M.S.), Yamaguchi Educational and Scholarship Foundation (M.S.), and also the Platform Project for Supporting Drug Discovery and Life Science Research funded by Japan Agency for Medical Research and Development (AMED) (M.S., K.N.K., and Y.K.). Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

year = "2019",

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doi = "10.1021/acs.orglett.9b00550",

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Shigeno, M, Nakaji, K, Nozawa-Kumada, K & Kondo, Y 2019, ' Catalytic Amide-Base System of TMAF and N(TMS) ₃ for Deprotonative Coupling of Benzylic C(sp ³ )-H Bonds with Carbonyls ', Organic Letters, vol. 21, no. 8, pp. 2588-2592. https://doi.org/10.1021/acs.orglett.9b00550

Catalytic Amide-Base System of TMAF and N(TMS) ₃ for Deprotonative Coupling of Benzylic C(sp ³ )-H Bonds with Carbonyls . / Shigeno, Masanori; Nakaji, Kunihito; Nozawa-Kumada, Kanako et al.
In: Organic Letters, Vol. 21, No. 8, 19.04.2019, p. 2588-2592.

Research output: Contribution to journal › Article › peer-review

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T1 - Catalytic Amide-Base System of TMAF and N(TMS) 3 for Deprotonative Coupling of Benzylic C(sp 3 )-H Bonds with Carbonyls

AU - Shigeno, Masanori

AU - Nakaji, Kunihito

AU - Nozawa-Kumada, Kanako

AU - Kondo, Yoshinori

N1 - Funding Information: This work was financially supported by JSPS KAKENHI Grant No. 16H00997 in Precisely Designed Catalysts with Customized Scaffolding (Y.K.), JSPS KAKENHI Grant No. 17K15419 (M.S.), Grand for Basic Science Research Projects from The Sumitomo Foundation (M.S.), Yamaguchi Educational and Scholarship Foundation (M.S.), and also the Platform Project for Supporting Drug Discovery and Life Science Research funded by Japan Agency for Medical Research and Development (AMED) (M.S., K.N.K., and Y.K.). Publisher Copyright: Copyright © 2019 American Chemical Society.

PY - 2019/4/19

Y1 - 2019/4/19

N2 - This paper describes that an amide-base generated in situ from tetramethylammonium fluoride (TMAF) and N(TMS) 3 catalyzes the deprotonative coupling of benzylic C(sp 3 )-H bonds with carbonyls to form stilbenes. A variety of methylheteroarenes (2-methylbenzothiophene, 2-methylbenzofuran, and 2-, 3-, or 4-methylpyridines) are used as nucleophiles. Application to enamine synthesis using DMF as an electrophile is also shown. The present system is effective for toluenes (4-phenyl-, 4-bromo-, 2-bromo-, and 4-chlorotoluenes) having low reactivity.

AB - This paper describes that an amide-base generated in situ from tetramethylammonium fluoride (TMAF) and N(TMS) 3 catalyzes the deprotonative coupling of benzylic C(sp 3 )-H bonds with carbonyls to form stilbenes. A variety of methylheteroarenes (2-methylbenzothiophene, 2-methylbenzofuran, and 2-, 3-, or 4-methylpyridines) are used as nucleophiles. Application to enamine synthesis using DMF as an electrophile is also shown. The present system is effective for toluenes (4-phenyl-, 4-bromo-, 2-bromo-, and 4-chlorotoluenes) having low reactivity.

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JO - Organic Letters

JF - Organic Letters

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Shigeno M, Nakaji K, Nozawa-Kumada K, Kondo Y. Catalytic Amide-Base System of TMAF and N(TMS) ₃ for Deprotonative Coupling of Benzylic C(sp ³ )-H Bonds with Carbonyls Organic Letters. 2019 Apr 19;21(8):2588-2592. doi: 10.1021/acs.orglett.9b00550

Catalytic Amide-Base System of TMAF and N(TMS) ₃ for Deprotonative Coupling of Benzylic C(sp ³ )-H Bonds with Carbonyls

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