Stereoselective synthesis and reactions of secondary alkyllithium reagents functionalized at the 3-position

Kohei Moriya, Dorian Didier, Meike Simon, Jeffrey M. Hammann, Guillaume Berionni, Konstantin Karaghiosoff, Hendrik Zipse, Herbert Mayr, Paul Knochel, K. Moriya, D. Didier, M. Simon, J. M. Hammann, Guillaume Berionni, Prof K. Karaghiosoff, Prof H. Zipse, Prof H. Mayr, Prof P. Knochel

Research output: Contribution to journalArticle

Abstract

Secondary alkyllithium reagents bearing an OTBS group (TBS = tert-butyldimethylsilyl) at the 3-position can be prepared stereoconvergently through an I/Li exchange from a diastereomeric mixture of the corresponding secondary alkyl iodides. These lithium reagents react with a range of electrophiles, including carbon electrophiles, with retention of configuration to yield various 1,3-difunctionalized derivatives with good diastereoselectivities. Kinetic studies show that the 3- siloxy group strongly accelerates the epimerization at the lithium-substituted carbon atom. This method offers a new way to construct chiral open-chain molecules with excellent stereoselectivity.

Original languageEnglish
Pages (from-to)2754-2757
Number of pages4
JournalAngewandte Chemie - International Edition
Volume54
Issue number9
DOIs
Publication statusPublished - 23 Feb 2015
Externally publishedYes

Fingerprint

Lithium
Bearings (structural)
Carbon
Stereoselectivity
Iodides
Derivatives
Atoms
Molecules
Kinetics

Keywords

  • Carbanions
  • Diastereoselectivity
  • Kinetics
  • Lithiation
  • Nucleophilic substitution

Cite this

Moriya, Kohei ; Didier, Dorian ; Simon, Meike ; Hammann, Jeffrey M. ; Berionni, Guillaume ; Karaghiosoff, Konstantin ; Zipse, Hendrik ; Mayr, Herbert ; Knochel, Paul ; Moriya, K. ; Didier, D. ; Simon, M. ; Hammann, J. M. ; Berionni, Guillaume ; Karaghiosoff, Prof K. ; Zipse, Prof H. ; Mayr, Prof H. ; Knochel, Prof P. / Stereoselective synthesis and reactions of secondary alkyllithium reagents functionalized at the 3-position. In: Angewandte Chemie - International Edition. 2015 ; Vol. 54, No. 9. pp. 2754-2757.
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abstract = "Secondary alkyllithium reagents bearing an OTBS group (TBS = tert-butyldimethylsilyl) at the 3-position can be prepared stereoconvergently through an I/Li exchange from a diastereomeric mixture of the corresponding secondary alkyl iodides. These lithium reagents react with a range of electrophiles, including carbon electrophiles, with retention of configuration to yield various 1,3-difunctionalized derivatives with good diastereoselectivities. Kinetic studies show that the 3- siloxy group strongly accelerates the epimerization at the lithium-substituted carbon atom. This method offers a new way to construct chiral open-chain molecules with excellent stereoselectivity.",
keywords = "Carbanions, Diastereoselectivity, Kinetics, Lithiation, Nucleophilic substitution",
author = "Kohei Moriya and Dorian Didier and Meike Simon and Hammann, {Jeffrey M.} and Guillaume Berionni and Konstantin Karaghiosoff and Hendrik Zipse and Herbert Mayr and Paul Knochel and K. Moriya and D. Didier and M. Simon and Hammann, {J. M.} and Guillaume Berionni and Karaghiosoff, {Prof K.} and Zipse, {Prof H.} and Mayr, {Prof H.} and Knochel, {Prof P.}",
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Moriya, K, Didier, D, Simon, M, Hammann, JM, Berionni, G, Karaghiosoff, K, Zipse, H, Mayr, H, Knochel, P, Moriya, K, Didier, D, Simon, M, Hammann, JM, Berionni, G, Karaghiosoff, PK, Zipse, PH, Mayr, PH & Knochel, PP 2015, 'Stereoselective synthesis and reactions of secondary alkyllithium reagents functionalized at the 3-position', Angewandte Chemie - International Edition, vol. 54, no. 9, pp. 2754-2757. https://doi.org/10.1002/anie.201409165

Stereoselective synthesis and reactions of secondary alkyllithium reagents functionalized at the 3-position. / Moriya, Kohei; Didier, Dorian; Simon, Meike; Hammann, Jeffrey M.; Berionni, Guillaume; Karaghiosoff, Konstantin; Zipse, Hendrik; Mayr, Herbert; Knochel, Paul; Moriya, K.; Didier, D.; Simon, M.; Hammann, J. M.; Berionni, Guillaume; Karaghiosoff, Prof K.; Zipse, Prof H.; Mayr, Prof H.; Knochel, Prof P.

In: Angewandte Chemie - International Edition, Vol. 54, No. 9, 23.02.2015, p. 2754-2757.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Stereoselective synthesis and reactions of secondary alkyllithium reagents functionalized at the 3-position

AU - Moriya, Kohei

AU - Didier, Dorian

AU - Simon, Meike

AU - Hammann, Jeffrey M.

AU - Berionni, Guillaume

AU - Karaghiosoff, Konstantin

AU - Zipse, Hendrik

AU - Mayr, Herbert

AU - Knochel, Paul

AU - Moriya, K.

AU - Didier, D.

AU - Simon, M.

AU - Hammann, J. M.

AU - Berionni, Guillaume

AU - Karaghiosoff, Prof K.

AU - Zipse, Prof H.

AU - Mayr, Prof H.

AU - Knochel, Prof P.

PY - 2015/2/23

Y1 - 2015/2/23

N2 - Secondary alkyllithium reagents bearing an OTBS group (TBS = tert-butyldimethylsilyl) at the 3-position can be prepared stereoconvergently through an I/Li exchange from a diastereomeric mixture of the corresponding secondary alkyl iodides. These lithium reagents react with a range of electrophiles, including carbon electrophiles, with retention of configuration to yield various 1,3-difunctionalized derivatives with good diastereoselectivities. Kinetic studies show that the 3- siloxy group strongly accelerates the epimerization at the lithium-substituted carbon atom. This method offers a new way to construct chiral open-chain molecules with excellent stereoselectivity.

AB - Secondary alkyllithium reagents bearing an OTBS group (TBS = tert-butyldimethylsilyl) at the 3-position can be prepared stereoconvergently through an I/Li exchange from a diastereomeric mixture of the corresponding secondary alkyl iodides. These lithium reagents react with a range of electrophiles, including carbon electrophiles, with retention of configuration to yield various 1,3-difunctionalized derivatives with good diastereoselectivities. Kinetic studies show that the 3- siloxy group strongly accelerates the epimerization at the lithium-substituted carbon atom. This method offers a new way to construct chiral open-chain molecules with excellent stereoselectivity.

KW - Carbanions

KW - Diastereoselectivity

KW - Kinetics

KW - Lithiation

KW - Nucleophilic substitution

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U2 - 10.1002/anie.201409165

DO - 10.1002/anie.201409165

M3 - Article

VL - 54

SP - 2754

EP - 2757

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

SN - 1521-3773

IS - 9

ER -