Amines bearing tertiary substituents by tandem enantioselective carbolithiation-rearrangement of vinylureas

Michael Tait; Morgan Donnard; Alberto Minassi; Julien Lefranc; Beatrice Bechi; Giorgio Carbone; Peter O'Brien; Jonathan Clayden

doi:10.1021/ol3029324

Amines bearing tertiary substituents by tandem enantioselective carbolithiation-rearrangement of vinylureas

Michael Tait, Morgan Donnard, Alberto Minassi, Julien Lefranc, Beatrice Bechi, Giorgio Carbone, Peter O'Brien, Jonathan Clayden^*

^*Corresponding author for this work

School of Chemistry

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

38 Citations (Scopus)

Abstract

In the presence of (-)-sparteine or a (+)-sparteine surrogate, organolithiums add to N-alkenyl-N'-arylureas to give benzylic organolithiums in an enantioselective manner. Under the influence of DMPU, these organolithiums undergo rearrangement with migration of the N'-aryl ring from N to C, leading to the urea derivatives of enantiomerically enriched amines bearing tertiary substituents. Basic hydrolysis returns the functionalized amine, providing a new synthetic route to compounds with quaternary stereogenic centers bearing nitrogen.

Original language	English
Pages (from-to)	34-37
Number of pages	4
Journal	Organic Letters
Volume	15
Issue number	1
Early online date	19 Dec 2012
DOIs	https://doi.org/10.1021/ol3029324
Publication status	Published - 4 Jan 2013

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title = "Amines bearing tertiary substituents by tandem enantioselective carbolithiation-rearrangement of vinylureas",

abstract = "In the presence of (-)-sparteine or a (+)-sparteine surrogate, organolithiums add to N-alkenyl-N'-arylureas to give benzylic organolithiums in an enantioselective manner. Under the influence of DMPU, these organolithiums undergo rearrangement with migration of the N'-aryl ring from N to C, leading to the urea derivatives of enantiomerically enriched amines bearing tertiary substituents. Basic hydrolysis returns the functionalized amine, providing a new synthetic route to compounds with quaternary stereogenic centers bearing nitrogen.",

author = "Michael Tait and Morgan Donnard and Alberto Minassi and Julien Lefranc and Beatrice Bechi and Giorgio Carbone and Peter O'Brien and Jonathan Clayden",

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T1 - Amines bearing tertiary substituents by tandem enantioselective carbolithiation-rearrangement of vinylureas

AU - Tait, Michael

AU - Donnard, Morgan

AU - Minassi, Alberto

AU - Lefranc, Julien

AU - Bechi, Beatrice

AU - Carbone, Giorgio

AU - O'Brien, Peter

AU - Clayden, Jonathan

PY - 2013/1/4

Y1 - 2013/1/4

N2 - In the presence of (-)-sparteine or a (+)-sparteine surrogate, organolithiums add to N-alkenyl-N'-arylureas to give benzylic organolithiums in an enantioselective manner. Under the influence of DMPU, these organolithiums undergo rearrangement with migration of the N'-aryl ring from N to C, leading to the urea derivatives of enantiomerically enriched amines bearing tertiary substituents. Basic hydrolysis returns the functionalized amine, providing a new synthetic route to compounds with quaternary stereogenic centers bearing nitrogen.

AB - In the presence of (-)-sparteine or a (+)-sparteine surrogate, organolithiums add to N-alkenyl-N'-arylureas to give benzylic organolithiums in an enantioselective manner. Under the influence of DMPU, these organolithiums undergo rearrangement with migration of the N'-aryl ring from N to C, leading to the urea derivatives of enantiomerically enriched amines bearing tertiary substituents. Basic hydrolysis returns the functionalized amine, providing a new synthetic route to compounds with quaternary stereogenic centers bearing nitrogen.

UR - http://www.scopus.com/inward/record.url?scp=84874080511&partnerID=8YFLogxK

U2 - 10.1021/ol3029324

DO - 10.1021/ol3029324

M3 - Article (Academic Journal)

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AN - SCOPUS:84874080511

SN - 1523-7060

VL - 15

SP - 34

EP - 37

JO - Organic Letters

JF - Organic Letters

IS - 1

ER -

Amines bearing tertiary substituents by tandem enantioselective carbolithiation-rearrangement of vinylureas

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