Substituent effects on axial chirality in 1-aryl-3,4-dihydroisoquinolines: controlling the rate of bond rotation

Josep Mas Roselló; Samantha Staniland; Nicholas J. Turner; Jonathan Clayden

doi:10.1016/j.tet.2016.01.037

Substituent effects on axial chirality in 1-aryl-3,4-dihydroisoquinolines: controlling the rate of bond rotation

Josep Mas Roselló, Samantha Staniland, Nicholas J. Turner, Jonathan Clayden^*

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

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Abstract

A series of 1-aryl-3,4-dihydroisoquinolines (DHIQs) were synthesized and their barriers to bond rotation were determined by means of VT-NMR, dynamic HPLC or racemization studies. Although they all presented lower rotational stability than the related 1-arylisoquinolines (such as QUINAP), certain 1-aryl-DHIQ structures had a sufficiently high barrier to bond rotation to show axial chirality. These compounds included 1-(2-triflyl-1-naphthyl)-4,5-dihydroisoquinoline 4h and 1-(2-diphenylphosphanyl-1-naphthyl)-4,5-dihydroisoquinoline 4i. This discovery opens the door to the development of a new group of axially chiral N,P ligands for asymmetric synthesis and also potentially to new strategies for the synthesis of axially chiral 1-arylisoquinolines.

Original language	English
Pages (from-to)	5172-5177
Number of pages	6
Journal	Tetrahedron
Volume	72
Issue number	34
Early online date	21 Jan 2016
DOIs	https://doi.org/10.1016/j.tet.2016.01.037
Publication status	Published - 25 Aug 2016

Bibliographical note

Special issue: Methods for controlling axial chirality

Keywords

Atropisomers
Axial chirality
Biaryls
Dihydroisoquinolines
QUINAP

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Accepted author manuscript, 1.39 MBLicence: CC BY-NC-ND

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title = "Substituent effects on axial chirality in 1-aryl-3,4-dihydroisoquinolines: controlling the rate of bond rotation",

abstract = "A series of 1-aryl-3,4-dihydroisoquinolines (DHIQs) were synthesized and their barriers to bond rotation were determined by means of VT-NMR, dynamic HPLC or racemization studies. Although they all presented lower rotational stability than the related 1-arylisoquinolines (such as QUINAP), certain 1-aryl-DHIQ structures had a sufficiently high barrier to bond rotation to show axial chirality. These compounds included 1-(2-triflyl-1-naphthyl)-4,5-dihydroisoquinoline 4h and 1-(2-diphenylphosphanyl-1-naphthyl)-4,5-dihydroisoquinoline 4i. This discovery opens the door to the development of a new group of axially chiral N,P ligands for asymmetric synthesis and also potentially to new strategies for the synthesis of axially chiral 1-arylisoquinolines.",

keywords = "Atropisomers, Axial chirality, Biaryls, Dihydroisoquinolines, QUINAP",

author = "Rosell{\'o}, {Josep Mas} and Samantha Staniland and Turner, {Nicholas J.} and Jonathan Clayden",

note = "Special issue: Methods for controlling axial chirality",

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doi = "10.1016/j.tet.2016.01.037",

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T1 - Substituent effects on axial chirality in 1-aryl-3,4-dihydroisoquinolines

T2 - controlling the rate of bond rotation

AU - Roselló, Josep Mas

AU - Staniland, Samantha

AU - Turner, Nicholas J.

AU - Clayden, Jonathan

N1 - Special issue: Methods for controlling axial chirality

PY - 2016/8/25

Y1 - 2016/8/25

N2 - A series of 1-aryl-3,4-dihydroisoquinolines (DHIQs) were synthesized and their barriers to bond rotation were determined by means of VT-NMR, dynamic HPLC or racemization studies. Although they all presented lower rotational stability than the related 1-arylisoquinolines (such as QUINAP), certain 1-aryl-DHIQ structures had a sufficiently high barrier to bond rotation to show axial chirality. These compounds included 1-(2-triflyl-1-naphthyl)-4,5-dihydroisoquinoline 4h and 1-(2-diphenylphosphanyl-1-naphthyl)-4,5-dihydroisoquinoline 4i. This discovery opens the door to the development of a new group of axially chiral N,P ligands for asymmetric synthesis and also potentially to new strategies for the synthesis of axially chiral 1-arylisoquinolines.

AB - A series of 1-aryl-3,4-dihydroisoquinolines (DHIQs) were synthesized and their barriers to bond rotation were determined by means of VT-NMR, dynamic HPLC or racemization studies. Although they all presented lower rotational stability than the related 1-arylisoquinolines (such as QUINAP), certain 1-aryl-DHIQ structures had a sufficiently high barrier to bond rotation to show axial chirality. These compounds included 1-(2-triflyl-1-naphthyl)-4,5-dihydroisoquinoline 4h and 1-(2-diphenylphosphanyl-1-naphthyl)-4,5-dihydroisoquinoline 4i. This discovery opens the door to the development of a new group of axially chiral N,P ligands for asymmetric synthesis and also potentially to new strategies for the synthesis of axially chiral 1-arylisoquinolines.

KW - Atropisomers

KW - Axial chirality

KW - Biaryls

KW - Dihydroisoquinolines

KW - QUINAP

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U2 - 10.1016/j.tet.2016.01.037

DO - 10.1016/j.tet.2016.01.037

M3 - Article (Academic Journal)

AN - SCOPUS:84979655941

SN - 0040-4020

VL - 72

SP - 5172

EP - 5177

JO - Tetrahedron

JF - Tetrahedron

IS - 34

ER -

Substituent effects on axial chirality in 1-aryl-3,4-dihydroisoquinolines: controlling the rate of bond rotation

Abstract

Bibliographical note

Keywords

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