Site-selective C–H arylation of primary aliphatic amines enabled by a catalytic transient directing group

A Pdᴵᴵ-catalyzed, ligand-enabled gamma-C(sp3)–H arylation of free primary aliphatic amines and amino esters without using an exogenous directing group is reported. This reaction is compatible with unhindered free aliphatic amines, and it is also be applicable to the rapid synthesis of biologically and synthetically valuable unnatural α-amino acids. Large scale synthesis is also feasible using this method.

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Native amine-directed site-selective C(sp3)-H arylation of primary aliphatic amines with aryl iodides

Chinese Chemical Letters ◽

10.1016/j.cclet.2019.10.034 ◽

2020 ◽

Vol 31 (5) ◽

pp. 1327-1331 ◽

Cited By ~ 3

Author(s):

Pranab K. Pramanick ◽

Zhibing Zhou ◽

Zhenlin Hou ◽

Yufei Ao ◽

Bo Yao

Keyword(s):

Aliphatic Amines ◽

Aryl Iodides ◽

Site Selective ◽

Primary Aliphatic Amines

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Exogenous Directing Group Free, Ligand-Enabled gamma-C(sp3)–H Arylation of Free Primary Aliphatic Amines and α-Amino Esters

10.26434/chemrxiv.11301017.v1 ◽

2019 ◽

Author(s):

Yongzheng Ding ◽

Shuai Fan ◽

Xiaoxi Chen ◽

yuzhen gao ◽

Gang Li

Keyword(s):

Amino Acids ◽

Large Scale ◽

Free Ligand ◽

Aliphatic Amines ◽

Rapid Synthesis ◽

Amino Esters ◽

Directing Group ◽

Large Scale Synthesis ◽

Primary Aliphatic Amines

A Pdᴵᴵ-catalyzed, ligand-enabled gamma-C(sp3)–H arylation of free primary aliphatic amines and amino esters without using an exogenous directing group is reported. This reaction is compatible with unhindered free aliphatic amines, and it is also be applicable to the rapid synthesis of biologically and synthetically valuable unnatural α-amino acids. Large scale synthesis is also feasible using this method.

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para-Selective Cyanation of Arenes by H-Bonded Template

10.26434/chemrxiv.11448690.v1 ◽

2019 ◽

Author(s):

Sandeep Pimparkar ◽

Trisha Bhattacharya ◽

Arun Maji ◽

Argha Saha ◽

Ramasamy Jayarajan ◽

...

Keyword(s):

Selective Functionalization ◽

Directing Group ◽

Product Utility ◽

Site Selective

The significance of site selective functionalization stands upon the superior selectivity, easy synthesis and diverse product utility. In this work we demonstrate the para-selective introduction of versatile nitrile moiety, enabled by detachable and reusable H-bonded auxiliary. The methodology holds its efficiency irrespective of substrate electronic bias. The conspicuous shift in the step energetics was probed by both experimental and computational mechanistic tools heralds the inception of para-deuteration. The synthetic impact of the methodology was highlighted with reusability of directing group and post synthetic modifications

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para-Selective Cyanation of Arenes by H-Bonded Template

10.26434/chemrxiv.11448690 ◽

2019 ◽

Author(s):

Sandeep Pimparkar ◽

Trisha Bhattacharya ◽

Arun Maji ◽

Argha Saha ◽

Ramasamy Jayarajan ◽

...

Keyword(s):

Selective Functionalization ◽

Directing Group ◽

Product Utility ◽

Site Selective

The significance of site selective functionalization stands upon the superior selectivity, easy synthesis and diverse product utility. In this work we demonstrate the para-selective introduction of versatile nitrile moiety, enabled by detachable and reusable H-bonded auxiliary. The methodology holds its efficiency irrespective of substrate electronic bias. The conspicuous shift in the step energetics was probed by both experimental and computational mechanistic tools heralds the inception of para-deuteration. The synthetic impact of the methodology was highlighted with reusability of directing group and post synthetic modifications

Download Full-text