Stereospecificity and stereoselectivity in electrophilic substitution reactions of non-α-heterosubstituted organolithiums and stannanes: A rotationally restricted amide as an internal stereochemical marker

J. Clayden; M. Helliwell; J. H. Pink; N. Westlund

doi:10.1021/ja0112590

Stereospecificity and stereoselectivity in electrophilic substitution reactions of non-α-heterosubstituted organolithiums and stannanes: A rotationally restricted amide as an internal stereochemical marker

J. Clayden, M. Helliwell, J. H. Pink, N. Westlund

Research output: Contribution to journal › Article › peer-review

Abstract

The complete stereochemical course of a tin-lithium exchange/electrophilic quench sequence has been unambiguously determined by stereochemical characterization (using X-ray crystallography or NOE studies) at every step. Pairs of diastereoisomeric stannanes of known stereochemistry bearing atropisomeric amide substituents undergo tin-lithium exchange with alkyllithiums to give diastereoisometic benzylic organolithiums whose stereochemistry can be assigned by NMR. For one atropisomer of the stannanes, the tin-lithium exchange is fully stereospecific and proceeds with retention of stereochemistry. The other atropisomer undergoes nonstereospecific tin-lithium exchange: The first reported example of a lack of stereospecificity in electrophilic substitution of tin for lithium. One of the diastereoisomeric atropisomeric organolithiums produced by the tin-lithium exchange is deuterated and alkylated with retention but stannylated with inversion of stereochemistry. The other is alkylated nonstereospecifically but stannylated with retention.

Original language	English
Pages (from-to)	12449-12457
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	123
Issue number	50
DOIs	https://doi.org/10.1021/ja0112590
Publication status	Published - 19 Dec 2001

Keywords

Crystal structure; Molecular structure (of alkyl and stannyl naphthamides); Asymmetric synthesis and induction; Overhauser effect (stereospecificity and stereoselectivity in electrophilic substitution reactions of non-heterosubstituted organolithiums and stannanes and rotationally restricted amide as internal stereochem. marker); Substitution reaction (tin-lithium exchange; stereospecificity and stereoselectivity in electrophilic substitution reactions of non-heterosubstituted organolithiums and stannanes and rotationally restricted amide as internal stereochem. marker)

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CCDC 177032: Experimental Crystal Structure Determination
Clayden, J. (Contributor), Helliwell, M. (Contributor), Pink, J. H. (Contributor) & Westlund, N. (Contributor), Cambridge Crystallographic Data Centre, 2002
DOI: 10.5517/cc5y6q0, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc5y6q0&sid=DataCite
Dataset
CCDC 177033: Experimental Crystal Structure Determination
Clayden, J. (Contributor), Helliwell, M. (Contributor), Pink, J. H. (Contributor) & Westlund, N. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2002
DOI: 10.5517/cc5y6r1, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc5y6r1&sid=DataCite
Dataset

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@article{aec4e6fec4ee4647ae621d1858dd8caf,

title = "Stereospecificity and stereoselectivity in electrophilic substitution reactions of non-α-heterosubstituted organolithiums and stannanes: A rotationally restricted amide as an internal stereochemical marker",

abstract = "The complete stereochemical course of a tin-lithium exchange/electrophilic quench sequence has been unambiguously determined by stereochemical characterization (using X-ray crystallography or NOE studies) at every step. Pairs of diastereoisomeric stannanes of known stereochemistry bearing atropisomeric amide substituents undergo tin-lithium exchange with alkyllithiums to give diastereoisometic benzylic organolithiums whose stereochemistry can be assigned by NMR. For one atropisomer of the stannanes, the tin-lithium exchange is fully stereospecific and proceeds with retention of stereochemistry. The other atropisomer undergoes nonstereospecific tin-lithium exchange: The first reported example of a lack of stereospecificity in electrophilic substitution of tin for lithium. One of the diastereoisomeric atropisomeric organolithiums produced by the tin-lithium exchange is deuterated and alkylated with retention but stannylated with inversion of stereochemistry. The other is alkylated nonstereospecifically but stannylated with retention.",

keywords = "Crystal structure; Molecular structure (of alkyl and stannyl naphthamides); Asymmetric synthesis and induction; Overhauser effect (stereospecificity and stereoselectivity in electrophilic substitution reactions of non-heterosubstituted organolithiums and stannanes and rotationally restricted amide as internal stereochem. marker); Substitution reaction (tin-lithium exchange; stereospecificity and stereoselectivity in electrophilic substitution reactions of non-heterosubstituted organolithiums and stannanes and rotationally restricted amide as internal stereochem. marker)",

author = "J. Clayden and M. Helliwell and Pink, {J. H.} and N. Westlund",

year = "2001",

month = dec,

day = "19",

doi = "10.1021/ja0112590",

language = "English",

volume = "123",

pages = "12449--12457",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "50",

}

Clayden, J, Helliwell, M, Pink, JH & Westlund, N 2001, 'Stereospecificity and stereoselectivity in electrophilic substitution reactions of non-α-heterosubstituted organolithiums and stannanes: A rotationally restricted amide as an internal stereochemical marker', Journal of the American Chemical Society, vol. 123, no. 50, pp. 12449-12457. https://doi.org/10.1021/ja0112590

Stereospecificity and stereoselectivity in electrophilic substitution reactions of non-α-heterosubstituted organolithiums and stannanes: A rotationally restricted amide as an internal stereochemical marker. / Clayden, J.; Helliwell, M.; Pink, J. H. et al.
In: Journal of the American Chemical Society, Vol. 123, No. 50, 19.12.2001, p. 12449-12457.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Stereospecificity and stereoselectivity in electrophilic substitution reactions of non-α-heterosubstituted organolithiums and stannanes: A rotationally restricted amide as an internal stereochemical marker

AU - Clayden, J.

AU - Helliwell, M.

AU - Pink, J. H.

AU - Westlund, N.

PY - 2001/12/19

Y1 - 2001/12/19

N2 - The complete stereochemical course of a tin-lithium exchange/electrophilic quench sequence has been unambiguously determined by stereochemical characterization (using X-ray crystallography or NOE studies) at every step. Pairs of diastereoisomeric stannanes of known stereochemistry bearing atropisomeric amide substituents undergo tin-lithium exchange with alkyllithiums to give diastereoisometic benzylic organolithiums whose stereochemistry can be assigned by NMR. For one atropisomer of the stannanes, the tin-lithium exchange is fully stereospecific and proceeds with retention of stereochemistry. The other atropisomer undergoes nonstereospecific tin-lithium exchange: The first reported example of a lack of stereospecificity in electrophilic substitution of tin for lithium. One of the diastereoisomeric atropisomeric organolithiums produced by the tin-lithium exchange is deuterated and alkylated with retention but stannylated with inversion of stereochemistry. The other is alkylated nonstereospecifically but stannylated with retention.

AB - The complete stereochemical course of a tin-lithium exchange/electrophilic quench sequence has been unambiguously determined by stereochemical characterization (using X-ray crystallography or NOE studies) at every step. Pairs of diastereoisomeric stannanes of known stereochemistry bearing atropisomeric amide substituents undergo tin-lithium exchange with alkyllithiums to give diastereoisometic benzylic organolithiums whose stereochemistry can be assigned by NMR. For one atropisomer of the stannanes, the tin-lithium exchange is fully stereospecific and proceeds with retention of stereochemistry. The other atropisomer undergoes nonstereospecific tin-lithium exchange: The first reported example of a lack of stereospecificity in electrophilic substitution of tin for lithium. One of the diastereoisomeric atropisomeric organolithiums produced by the tin-lithium exchange is deuterated and alkylated with retention but stannylated with inversion of stereochemistry. The other is alkylated nonstereospecifically but stannylated with retention.

KW - Crystal structure; Molecular structure (of alkyl and stannyl naphthamides); Asymmetric synthesis and induction; Overhauser effect (stereospecificity and stereoselectivity in electrophilic substitution reactions of non-heterosubstituted organolithiums and

U2 - 10.1021/ja0112590

DO - 10.1021/ja0112590

M3 - Article

SN - 0002-7863

VL - 123

SP - 12449

EP - 12457

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 50

ER -

Stereospecificity and stereoselectivity in electrophilic substitution reactions of non-α-heterosubstituted organolithiums and stannanes: A rotationally restricted amide as an internal stereochemical marker

Abstract

Keywords

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Datasets

CCDC 177032: Experimental Crystal Structure Determination

CCDC 177033: Experimental Crystal Structure Determination

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