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Synthesis 2023; 55(16): 2547-2553
DOI: 10.1055/a-2055-2313
paper

Pd-Catalyzed MIA-Directed Methoxylation of Phenylalanines: A Combined Experimental and Computational Study

Wen-Jun Tang
a   School of Pharmaceutical Engineering, Zhejiang Pharmaceutical University, No 666 Siming road, Fenghua District, Ningbo 315599, P. R. of China
b   State Key Laboratory of Fine Chemicals, Ningbo Institute of Dalian University of Technology, No.26 Yucai Road, Jiangbei District, Ningbo 315016, P. R. of China
,
Shu-Min Dai
a   School of Pharmaceutical Engineering, Zhejiang Pharmaceutical University, No 666 Siming road, Fenghua District, Ningbo 315599, P. R. of China
b   State Key Laboratory of Fine Chemicals, Ningbo Institute of Dalian University of Technology, No.26 Yucai Road, Jiangbei District, Ningbo 315016, P. R. of China
,
Yue Yuan
a   School of Pharmaceutical Engineering, Zhejiang Pharmaceutical University, No 666 Siming road, Fenghua District, Ningbo 315599, P. R. of China
b   State Key Laboratory of Fine Chemicals, Ningbo Institute of Dalian University of Technology, No.26 Yucai Road, Jiangbei District, Ningbo 315016, P. R. of China
,
Shuai Wang
a   School of Pharmaceutical Engineering, Zhejiang Pharmaceutical University, No 666 Siming road, Fenghua District, Ningbo 315599, P. R. of China
,
Yu-Peng He
a   School of Pharmaceutical Engineering, Zhejiang Pharmaceutical University, No 666 Siming road, Fenghua District, Ningbo 315599, P. R. of China
b   State Key Laboratory of Fine Chemicals, Ningbo Institute of Dalian University of Technology, No.26 Yucai Road, Jiangbei District, Ningbo 315016, P. R. of China
,
Fang Yu  ∗
a   School of Pharmaceutical Engineering, Zhejiang Pharmaceutical University, No 666 Siming road, Fenghua District, Ningbo 315599, P. R. of China
b   State Key Laboratory of Fine Chemicals, Ningbo Institute of Dalian University of Technology, No.26 Yucai Road, Jiangbei District, Ningbo 315016, P. R. of China
c   Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning Petrochemical University, Dandong Road West 1, Fushun 113001, Liaoning, P. R. of China
› Author AffiliationsWe are grateful for the financial support from the National Natural Science Foundation of China (grant No. 21978124) and Key Projects of Ningbo Natural Science Foundation (grant No. 2022J003).
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Abstract

The direct methoxylation of substituted phenylalanines has been accomplished via methoxyiminoacyl (MIA)-mediated Pd-catalyzed C–H functionalization. A diverse array of ortho-methoxylated phenylalanine derivatives are efficiently generated in good to high yields. KIE study has shown that the oxhydryl cleavage step is the rate-limiting step. The computational data show that the participation manner of methanol has a great influence on the energy barriers of transition states during the C(sp2)–O formation stage. The pathway containing stepwise deprotonation and reductive elimination is superior to that of a concerted deprotonation-methoxylation.

Key words

methoxylation - palladium catalyst - MIA-directing group - DFT study - hydrogenation

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2055-2313.
  • Supporting Information


Publication History

Received: 10 January 2023

Accepted after revision: 15 March 2023

Accepted Manuscript online:
15 March 2023

Article published online:
20 April 2023

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