PNP-Mn(I) Catalyzed Base Free <i>N</i>-Alkylation of Amines Using Alcohols

We report a Mn(I) pincer complex, [Mn(CO)<sub>3</sub>{<i>o</i>-Ph<sub>2</sub>PC<sub>6</sub>H<sub>4</sub>C(O)N(C<sub>6</sub>H<sub>4</sub>PPh<sub>2</sub>-<i>o</i>)}κ<sup>3</sup>-<i>P</i>,<i>N</i>,<i>P</i>], bearing an amide-functionalized bisphosphine (BalaHariPhos), for the efficient <i>N</i>-alkylation of amines with alcohols. The reaction proceeds under base-free conditions at 80 °C, affording <i>N</i>-alkylated products in good to excellent yields within 12 h. Broad substrate scope is demonstrated, including the synthesis of indoles and dibenzyl piperazine. Selective mono-<i>N</i>-methylation of amines using methanol as a C<sub>1</sub> source was also achieved. This work establishes a sustainable, non-noble metal platform for amine functionalization.

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Publication Details

Journal
Organic Letters
Published
2025-07-14
DOI
https://doi.org/10.1021/acs.orglett.5c02186
Citations
2
Primary Topic
Asymmetric Hydrogenation and Catalysis
Type
article
Field-Weighted Citation Impact
1.07
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article

PNP-Mn(I) Catalyzed Base Free N-Alkylation of Amines Using Alcohols

Maravanji S. Balakrishna, Rani Gourkhede
2 citations
Organic Letters
Asymmetric Hydrogenation and Catalysis
1.07
article

PNP-Mn(I) Catalyzed Base Free N-Alkylation of Amines Using Alcohols

Maravanji S. Balakrishna, Rani Gourkhede
article en
2 citations

Abstract

We report a Mn(I) pincer complex, [Mn(CO)<sub>3</sub>{<i>o</i>-Ph<sub>2</sub>PC<sub>6</sub>H<sub>4</sub>C(O)N(C<sub>6</sub>H<sub>4</sub>PPh<sub>2</sub>-<i>o</i>)}κ<sup>3</sup>-<i>P</i>,<i>N</i>,<i>P</i>], bearing an amide-functionalized bisphosphine (BalaHariPhos), for the efficient <i>N</i>-alkylation of amines with alcohols. The reaction proceeds under base-free conditions at 80 °C, affording <i>N</i>-alkylated products in good to excellent yields within 12 h. Broad substrate scope is demonstrated, including the synthesis of indoles and dibenzyl piperazine. Selective mono-<i>N</i>-methylation of amines using methanol as a C<sub>1</sub> source was also achieved. This work establishes a sustainable, non-noble metal platform for amine functionalization.

Organic LettersVol. 27(29)
Indian Institute of Technology Bombay (IN)
Clean water and sanitation
Openalex Percentile: Top 22%
Asymmetric Hydrogenation and Catalysis
1.07
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