Enantiospecific Synthesis of ortho-Substituted 1,1-Diarylalkanes by a 1,2-Metalate Rearrangement/anti-SN2′ Elimination/Rearomatizing Allylic Suzuki–Miyaura Reaction Sequence

Belén Rubial; Beatrice S.L. Collins; Raphael Bigler; Stefan Aichhorn; Adam Noble; Varinder K. Aggarwal

doi:10.1002/anie.201811343

Enantiospecific Synthesis of ortho-Substituted 1,1-Diarylalkanes by a 1,2-Metalate Rearrangement/anti-S_N2′ Elimination/Rearomatizing Allylic Suzuki–Miyaura Reaction Sequence

Belén Rubial, Beatrice S.L. Collins, Raphael Bigler, Stefan Aichhorn, Adam Noble, Varinder K. Aggarwal^*

^*Corresponding author for this work

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

12 Citations (Scopus)

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Abstract

The one‐pot sequential coupling of benzylamines, boronic esters and aryl iodides has been investigated. In the presence of an N‐activator, the boronate complex formed from an ortho‐lithiated benzylamine and a boronic ester undergoes stereospecific 1,2‐metalate rearrangement/anti‐SN2' elimination to form a dearomatized tertiary boronic ester. Treatment with an aryl iodide under palladium catalysis leads to rearomatizing γ‐selective allylic Suzuki‐Miyaura cross‐coupling to generate 1,1‐diarylalkanes. When enantioenriched α‐substituted benzylamines are employed, the corresponding 1,1‐diarylalkanes are formed with high stereospecificity.

Original language	English
Pages (from-to)	1366-1370
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	5
Early online date	21 Dec 2018
DOIs	https://doi.org/10.1002/anie.201811343
Publication status	Published - 28 Jan 2019

Keywords

1,1-diarylalkane
boronic ester
cross-coupling
one-pot
stereospecific

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Rubial, B., Collins, B. S. L., Bigler, R., Aichhorn, S., Noble, A., & Aggarwal, V. K. (2019). Enantiospecific Synthesis of ortho-Substituted 1,1-Diarylalkanes by a 1,2-Metalate Rearrangement/anti-S_N2′ Elimination/Rearomatizing Allylic Suzuki–Miyaura Reaction Sequence. Angewandte Chemie - International Edition, 58(5), 1366-1370. https://doi.org/10.1002/anie.201811343

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title = "Enantiospecific Synthesis of ortho-Substituted 1,1-Diarylalkanes by a 1,2-Metalate Rearrangement/anti-SN2′ Elimination/Rearomatizing Allylic Suzuki–Miyaura Reaction Sequence",

abstract = "The one‐pot sequential coupling of benzylamines, boronic esters and aryl iodides has been investigated. In the presence of an N‐activator, the boronate complex formed from an ortho‐lithiated benzylamine and a boronic ester undergoes stereospecific 1,2‐metalate rearrangement/anti‐SN2' elimination to form a dearomatized tertiary boronic ester. Treatment with an aryl iodide under palladium catalysis leads to rearomatizing γ‐selective allylic Suzuki‐Miyaura cross‐coupling to generate 1,1‐diarylalkanes. When enantioenriched α‐substituted benzylamines are employed, the corresponding 1,1‐diarylalkanes are formed with high stereospecificity.",

keywords = "1,1-diarylalkane, boronic ester, cross-coupling, one-pot, stereospecific",

author = "Bel{\'e}n Rubial and Collins, {Beatrice S.L.} and Raphael Bigler and Stefan Aichhorn and Adam Noble and Aggarwal, {Varinder K.}",

year = "2019",

month = jan,

day = "28",

doi = "10.1002/anie.201811343",

language = "English",

volume = "58",

pages = "1366--1370",

journal = "Angewandte Chemie - International Edition",

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publisher = "Wiley-VCH Verlag",

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Rubial, B, Collins, BSL, Bigler, R, Aichhorn, S, Noble, A & Aggarwal, VK 2019, 'Enantiospecific Synthesis of ortho-Substituted 1,1-Diarylalkanes by a 1,2-Metalate Rearrangement/anti-S_N2′ Elimination/Rearomatizing Allylic Suzuki–Miyaura Reaction Sequence', Angewandte Chemie - International Edition, vol. 58, no. 5, pp. 1366-1370. https://doi.org/10.1002/anie.201811343

Enantiospecific Synthesis of ortho-Substituted 1,1-Diarylalkanes by a 1,2-Metalate Rearrangement/anti-S_N2′ Elimination/Rearomatizing Allylic Suzuki–Miyaura Reaction Sequence. / Rubial, Belén; Collins, Beatrice S.L.; Bigler, Raphael et al.
In: Angewandte Chemie - International Edition, Vol. 58, No. 5, 28.01.2019, p. 1366-1370.

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

TY - JOUR

T1 - Enantiospecific Synthesis of ortho-Substituted 1,1-Diarylalkanes by a 1,2-Metalate Rearrangement/anti-SN2′ Elimination/Rearomatizing Allylic Suzuki–Miyaura Reaction Sequence

AU - Rubial, Belén

AU - Collins, Beatrice S.L.

AU - Bigler, Raphael

AU - Aichhorn, Stefan

AU - Noble, Adam

AU - Aggarwal, Varinder K.

PY - 2019/1/28

Y1 - 2019/1/28

N2 - The one‐pot sequential coupling of benzylamines, boronic esters and aryl iodides has been investigated. In the presence of an N‐activator, the boronate complex formed from an ortho‐lithiated benzylamine and a boronic ester undergoes stereospecific 1,2‐metalate rearrangement/anti‐SN2' elimination to form a dearomatized tertiary boronic ester. Treatment with an aryl iodide under palladium catalysis leads to rearomatizing γ‐selective allylic Suzuki‐Miyaura cross‐coupling to generate 1,1‐diarylalkanes. When enantioenriched α‐substituted benzylamines are employed, the corresponding 1,1‐diarylalkanes are formed with high stereospecificity.

AB - The one‐pot sequential coupling of benzylamines, boronic esters and aryl iodides has been investigated. In the presence of an N‐activator, the boronate complex formed from an ortho‐lithiated benzylamine and a boronic ester undergoes stereospecific 1,2‐metalate rearrangement/anti‐SN2' elimination to form a dearomatized tertiary boronic ester. Treatment with an aryl iodide under palladium catalysis leads to rearomatizing γ‐selective allylic Suzuki‐Miyaura cross‐coupling to generate 1,1‐diarylalkanes. When enantioenriched α‐substituted benzylamines are employed, the corresponding 1,1‐diarylalkanes are formed with high stereospecificity.

KW - 1,1-diarylalkane

KW - boronic ester

KW - cross-coupling

KW - one-pot

KW - stereospecific

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U2 - 10.1002/anie.201811343

DO - 10.1002/anie.201811343

M3 - Article (Academic Journal)

C2 - 30520228

SN - 1433-7851

VL - 58

SP - 1366

EP - 1370

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

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ER -

Enantiospecific Synthesis of ortho-Substituted 1,1-Diarylalkanes by a 1,2-Metalate Rearrangement/anti-S_N2′ Elimination/Rearomatizing Allylic Suzuki–Miyaura Reaction Sequence

Abstract

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FRESCO: Efficient, Flexible Synthesis of Molecules with Tailored Shapes: from Photoswitchable Helices to anti-Cancer Compounds

Changing the Synthesis Landscape with Boron at the Helm: from Chiral Organometallics to Assembly Line Synthesis

Dr Beatrice Collins

Dr Adam Noble

Cite this

Enantiospecific Synthesis of ortho-Substituted 1,1-Diarylalkanes by a 1,2-Metalate Rearrangement/anti-SN2′ Elimination/Rearomatizing Allylic Suzuki–Miyaura Reaction Sequence

Abstract

Keywords

Access to Document

Handle.net

Other files and links

Embargoed Document

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Projects

FRESCO: Efficient, Flexible Synthesis of Molecules with Tailored Shapes: from Photoswitchable Helices to anti-Cancer Compounds

Changing the Synthesis Landscape with Boron at the Helm: from Chiral Organometallics to Assembly Line Synthesis

Profiles

Dr Beatrice Collins

Dr Adam Noble

Cite this

Enantiospecific Synthesis of ortho-Substituted 1,1-Diarylalkanes by a 1,2-Metalate Rearrangement/anti-S_N2′ Elimination/Rearomatizing Allylic Suzuki–Miyaura Reaction Sequence