Rh-Catalyzed Enantioselective Allylation of N-Tosyl- and N-Nosylaldimines: Total Synthesis of (-)-Crispine A

Pei Fen Chiang; Wei Sian Li; Jia Hong Jian; Ting Shen Kuo; Ping Yu Wu; Hsyueh Liang Wu

doi:10.1021/acs.orglett.7b03523

Rh-Catalyzed Enantioselective Allylation of N-Tosyl- and N-Nosylaldimines: Total Synthesis of (-)-Crispine A

Pei Fen Chiang, Wei Sian Li, Jia Hong Jian, Ting Shen Kuo, Ping Yu Wu, Hsyueh Liang Wu^*

^*Corresponding author for this work

Department of Chemistry

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

26 Citations (Scopus)

Abstract

The unprecedented development of asymmetric Rh-catalyzed 1,2-allylation of N-Ts- and N-Ns-aldimines is achieved. This protocol utilizes potassium allyltrifluoroborates and various aldimines to generate enantioenriched homoallylic amines in the presence of 3.0 mol % of Rh(I)/L1b catalyst with up to 90% yield, 98% ee (R = H), and 10:1 diastereoselectivity (R = Me or Ph), yielding the same major diastereomer when using potassium (E)- and (Z)-crotyltrifluoroborate. Its synthetic utility is also illustrated in the total synthesis of (-)-crispine A.

Original language	English
Pages (from-to)	158-161
Number of pages	4
Journal	Organic Letters
Volume	20
Issue number	1
DOIs	https://doi.org/10.1021/acs.orglett.7b03523
Publication status	Published - 2018 Jan 5

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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10.1021/acs.orglett.7b03523

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title = "Rh-Catalyzed Enantioselective Allylation of N-Tosyl- and N-Nosylaldimines: Total Synthesis of (-)-Crispine A",

abstract = "The unprecedented development of asymmetric Rh-catalyzed 1,2-allylation of N-Ts- and N-Ns-aldimines is achieved. This protocol utilizes potassium allyltrifluoroborates and various aldimines to generate enantioenriched homoallylic amines in the presence of 3.0 mol % of Rh(I)/L1b catalyst with up to 90% yield, 98% ee (R = H), and 10:1 diastereoselectivity (R = Me or Ph), yielding the same major diastereomer when using potassium (E)- and (Z)-crotyltrifluoroborate. Its synthetic utility is also illustrated in the total synthesis of (-)-crispine A.",

author = "Chiang, {Pei Fen} and Li, {Wei Sian} and Jian, {Jia Hong} and Kuo, {Ting Shen} and Wu, {Ping Yu} and Wu, {Hsyueh Liang}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2018",

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day = "5",

doi = "10.1021/acs.orglett.7b03523",

language = "English",

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journal = "Organic Letters",

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T1 - Rh-Catalyzed Enantioselective Allylation of N-Tosyl- and N-Nosylaldimines

T2 - Total Synthesis of (-)-Crispine A

AU - Chiang, Pei Fen

AU - Li, Wei Sian

AU - Jian, Jia Hong

AU - Kuo, Ting Shen

AU - Wu, Ping Yu

AU - Wu, Hsyueh Liang

PY - 2018/1/5

Y1 - 2018/1/5

N2 - The unprecedented development of asymmetric Rh-catalyzed 1,2-allylation of N-Ts- and N-Ns-aldimines is achieved. This protocol utilizes potassium allyltrifluoroborates and various aldimines to generate enantioenriched homoallylic amines in the presence of 3.0 mol % of Rh(I)/L1b catalyst with up to 90% yield, 98% ee (R = H), and 10:1 diastereoselectivity (R = Me or Ph), yielding the same major diastereomer when using potassium (E)- and (Z)-crotyltrifluoroborate. Its synthetic utility is also illustrated in the total synthesis of (-)-crispine A.

AB - The unprecedented development of asymmetric Rh-catalyzed 1,2-allylation of N-Ts- and N-Ns-aldimines is achieved. This protocol utilizes potassium allyltrifluoroborates and various aldimines to generate enantioenriched homoallylic amines in the presence of 3.0 mol % of Rh(I)/L1b catalyst with up to 90% yield, 98% ee (R = H), and 10:1 diastereoselectivity (R = Me or Ph), yielding the same major diastereomer when using potassium (E)- and (Z)-crotyltrifluoroborate. Its synthetic utility is also illustrated in the total synthesis of (-)-crispine A.

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Rh-Catalyzed Enantioselective Allylation of N-Tosyl- and N-Nosylaldimines: Total Synthesis of (-)-Crispine A

Abstract

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CCDC 1585487: Experimental Crystal Structure Determination

CCDC 1585493: Experimental Crystal Structure Determination

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Rh-Catalyzed Enantioselective Allylation of N-Tosyl- and N-Nosylaldimines: Total Synthesis of (-)-Crispine A

Abstract

ASJC Scopus subject areas

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CCDC 1585487: Experimental Crystal Structure Determination

CCDC 1585493: Experimental Crystal Structure Determination

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