Complex Boron-Containing Molecules through a 1,2-Metalate Rearrangement/anti-S                         
                        N
                                                 2′ Elimination/Cycloaddition Reaction Sequence

Chloe Tillin; Raphael Bigler; Renata Calo-lapido; Beatrice Collins; Adam Noble; Varinder Aggarwal

doi:10.1055/s-0037-1610389

Complex Boron-Containing Molecules through a 1,2-Metalate Rearrangement/anti-S _N 2′ Elimination/Cycloaddition Reaction Sequence

Chloe Tillin, Raphael Bigler, Renata Calo-lapido, Beatrice Collins, Adam Noble, Varinder Aggarwal^*

^*Corresponding author for this work

School of Chemistry

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

7 Citations (Scopus)

521 Downloads (Pure)

Abstract

The three-component coupling of benzylamines, boronic esters, and 4-phenyl-3H-1,2,4-triazole-3,5(4H)-dione (PTAD) is reported. The boronate complex formed from an ortho-lithiated benzylamine and a boronic ester undergoes a stereospecific 1,2-metalate rearrangement/anti-S N 2′ elimination in the presence of an N-activator to provide a dearomatized tertiary boronic ester. Interception of this dearomatized intermediate with a dienophile leads to stereopredictable cycloaddition reactions to generate highly complex three-dimensional boron-containing molecular structures. When enantioenriched α-methyl-substituted benzylamines are employed, the corresponding cycloaddition adducts are formed with excellent enantiospecificities.

Original language	English
Pages (from-to)	449-453
Number of pages	5
Journal	SYNLETT
Volume	30
Issue number	4
Early online date	20 Nov 2018
DOIs	https://doi.org/10.1055/s-0037-1610389
Publication status	Published - 1 Jan 2019

Keywords

cycloaddition
1,2-metalate rearrangement
phenyltriazoledione
benzylamines
boronic esters
multicomponent reaction

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10.1055/s-0037-1610389

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This is the final published version of the article (version of record). It first appeared online via Thieme at https://www.thieme-connect.de/DOI/DOI?10.1055/s-0037-1610389 . Please refer to any applicable terms of use of the publisher.
Final published version, 5.29 MBLicence: CC BY-NC-ND

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Tillin, C., Bigler, R., Calo-lapido, R., Collins, B., Noble, A., & Aggarwal, V. (2019). Complex Boron-Containing Molecules through a 1,2-Metalate Rearrangement/anti-S _N 2′ Elimination/Cycloaddition Reaction Sequence. SYNLETT, 30(4), 449-453. https://doi.org/10.1055/s-0037-1610389

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title = "Complex Boron-Containing Molecules through a 1,2-Metalate Rearrangement/anti-S N 2′ Elimination/Cycloaddition Reaction Sequence",

abstract = "The three-component coupling of benzylamines, boronic esters, and 4-phenyl-3H-1,2,4-triazole-3,5(4H)-dione (PTAD) is reported. The boronate complex formed from an ortho-lithiated benzylamine and a boronic ester undergoes a stereospecific 1,2-metalate rearrangement/anti-S N 2′ elimination in the presence of an N-activator to provide a dearomatized tertiary boronic ester. Interception of this dearomatized intermediate with a dienophile leads to stereopredictable cycloaddition reactions to generate highly complex three-dimensional boron-containing molecular structures. When enantioenriched α-methyl-substituted benzylamines are employed, the corresponding cycloaddition adducts are formed with excellent enantiospecificities.",

keywords = "cycloaddition, 1,2-metalate rearrangement, phenyltriazoledione, benzylamines, boronic esters, multicomponent reaction",

author = "Chloe Tillin and Raphael Bigler and Renata Calo-lapido and Beatrice Collins and Adam Noble and Varinder Aggarwal",

year = "2019",

month = jan,

day = "1",

doi = "10.1055/s-0037-1610389",

language = "English",

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journal = "SYNLETT",

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Tillin, C, Bigler, R, Calo-lapido, R, Collins, B , Noble, A & Aggarwal, V 2019, 'Complex Boron-Containing Molecules through a 1,2-Metalate Rearrangement/anti-S _N 2′ Elimination/Cycloaddition Reaction Sequence', SYNLETT, vol. 30, no. 4, pp. 449-453. https://doi.org/10.1055/s-0037-1610389

Complex Boron-Containing Molecules through a 1,2-Metalate Rearrangement/anti-S _N 2′ Elimination/Cycloaddition Reaction Sequence. / Tillin, Chloe; Bigler, Raphael; Calo-lapido, Renata et al.
In: SYNLETT, Vol. 30, No. 4, 01.01.2019, p. 449-453.

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

TY - JOUR

T1 - Complex Boron-Containing Molecules through a 1,2-Metalate Rearrangement/anti-S N 2′ Elimination/Cycloaddition Reaction Sequence

AU - Tillin, Chloe

AU - Bigler, Raphael

AU - Calo-lapido, Renata

AU - Collins, Beatrice

AU - Noble, Adam

AU - Aggarwal, Varinder

PY - 2019/1/1

Y1 - 2019/1/1

N2 - The three-component coupling of benzylamines, boronic esters, and 4-phenyl-3H-1,2,4-triazole-3,5(4H)-dione (PTAD) is reported. The boronate complex formed from an ortho-lithiated benzylamine and a boronic ester undergoes a stereospecific 1,2-metalate rearrangement/anti-S N 2′ elimination in the presence of an N-activator to provide a dearomatized tertiary boronic ester. Interception of this dearomatized intermediate with a dienophile leads to stereopredictable cycloaddition reactions to generate highly complex three-dimensional boron-containing molecular structures. When enantioenriched α-methyl-substituted benzylamines are employed, the corresponding cycloaddition adducts are formed with excellent enantiospecificities.

AB - The three-component coupling of benzylamines, boronic esters, and 4-phenyl-3H-1,2,4-triazole-3,5(4H)-dione (PTAD) is reported. The boronate complex formed from an ortho-lithiated benzylamine and a boronic ester undergoes a stereospecific 1,2-metalate rearrangement/anti-S N 2′ elimination in the presence of an N-activator to provide a dearomatized tertiary boronic ester. Interception of this dearomatized intermediate with a dienophile leads to stereopredictable cycloaddition reactions to generate highly complex three-dimensional boron-containing molecular structures. When enantioenriched α-methyl-substituted benzylamines are employed, the corresponding cycloaddition adducts are formed with excellent enantiospecificities.

KW - cycloaddition

KW - 1,2-metalate rearrangement

KW - phenyltriazoledione

KW - benzylamines

KW - boronic esters

KW - multicomponent reaction

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U2 - 10.1055/s-0037-1610389

DO - 10.1055/s-0037-1610389

M3 - Letter (Academic Journal)

SN - 0936-5214

VL - 30

SP - 449

EP - 453

JO - SYNLETT

JF - SYNLETT

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ER -

Tillin C, Bigler R, Calo-lapido R, Collins B , Noble A , Aggarwal V. Complex Boron-Containing Molecules through a 1,2-Metalate Rearrangement/anti-S _N 2′ Elimination/Cycloaddition Reaction Sequence. SYNLETT. 2019 Jan 1;30(4):449-453. Epub 2018 Nov 20. doi: 10.1055/s-0037-1610389

Complex Boron-Containing Molecules through a 1,2-Metalate Rearrangement/anti-S _N 2′ Elimination/Cycloaddition 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

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Complex Boron-Containing Molecules through a 1,2-Metalate Rearrangement/anti-S N 2′ Elimination/Cycloaddition Reaction Sequence

Abstract

Keywords

Access to Document

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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

Cite this

Complex Boron-Containing Molecules through a 1,2-Metalate Rearrangement/anti-S _N 2′ Elimination/Cycloaddition Reaction Sequence