Scrambling of oxygen-18 during the "Borderline" solvolysis of 1-(3-nitrophenyl)ethyl tosylate

Yutaka Tsuji; Maria M. Toteva; Tina L. Amyes; John P. Richard

doi:10.1021/ol0484409

Scrambling of oxygen-18 during the "Borderline" solvolysis of 1-(3-nitrophenyl)ethyl tosylate

Yutaka Tsuji
, Maria M. Toteva
, Tina L. Amyes
, John P. Richard

Chemistry

National Institute of Technology, Kurume College
SUNY Buffalo

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

12 Scopus citations

Abstract

(Chemical Equation Presented) There is substantial isomerization (k _iso = 0.32 x 10^-3 s^-1) of 3-NO ₂C₆H₄¹³CH(Me)OS(¹⁸O) ²ToS during solvolysis (k_solv = 1.04 x 10^-3 s^-1) in 50/50 trifluoroethanol/water, even though the estimated lifetime of the putative 1-(3-nitrophenyl)ethyl carbocation intermediate of solvolysis (ca. 10^-13 s^-1) is too short to allow rearrangement that exchanges the positions of ¹⁶O and ¹⁸O at the sulfonate leaving group. This suggests that isomerization proceeds by a mechanism that avoids formation of the carbocation-anion pair intermediate.

Original language	English
Pages (from-to)	3633-3636
Number of pages	4
Journal	Organic Letters
Volume	6
Issue number	20
DOIs	https://doi.org/10.1021/ol0484409
State	Published - Sep 30 2004

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@article{6ed9a00a26154d4290fedf663f82ec5a,

title = "Scrambling of oxygen-18 during the {"}Borderline{"} solvolysis of 1-(3-nitrophenyl)ethyl tosylate",

abstract = "(Chemical Equation Presented) There is substantial isomerization (k iso = 0.32 x 10-3 s-1) of 3-NO 2C6H413CH(Me)OS(18O) 2ToS during solvolysis (ksolv = 1.04 x 10-3 s-1) in 50/50 trifluoroethanol/water, even though the estimated lifetime of the putative 1-(3-nitrophenyl)ethyl carbocation intermediate of solvolysis (ca. 10-13 s-1) is too short to allow rearrangement that exchanges the positions of 16O and 18O at the sulfonate leaving group. This suggests that isomerization proceeds by a mechanism that avoids formation of the carbocation-anion pair intermediate.",

author = "Yutaka Tsuji and Toteva, \{Maria M.\} and Amyes, \{Tina L.\} and Richard, \{John P.\}",

year = "2004",

month = sep,

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doi = "10.1021/ol0484409",

language = "English",

volume = "6",

pages = "3633--3636",

journal = "Organic Letters",

issn = "1523-7060",

publisher = "American Chemical Society",

number = "20",

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TY - JOUR

T1 - Scrambling of oxygen-18 during the "Borderline" solvolysis of 1-(3-nitrophenyl)ethyl tosylate

AU - Tsuji, Yutaka

AU - Toteva, Maria M.

AU - Amyes, Tina L.

AU - Richard, John P.

PY - 2004/9/30

Y1 - 2004/9/30

N2 - (Chemical Equation Presented) There is substantial isomerization (k iso = 0.32 x 10-3 s-1) of 3-NO 2C6H413CH(Me)OS(18O) 2ToS during solvolysis (ksolv = 1.04 x 10-3 s-1) in 50/50 trifluoroethanol/water, even though the estimated lifetime of the putative 1-(3-nitrophenyl)ethyl carbocation intermediate of solvolysis (ca. 10-13 s-1) is too short to allow rearrangement that exchanges the positions of 16O and 18O at the sulfonate leaving group. This suggests that isomerization proceeds by a mechanism that avoids formation of the carbocation-anion pair intermediate.

AB - (Chemical Equation Presented) There is substantial isomerization (k iso = 0.32 x 10-3 s-1) of 3-NO 2C6H413CH(Me)OS(18O) 2ToS during solvolysis (ksolv = 1.04 x 10-3 s-1) in 50/50 trifluoroethanol/water, even though the estimated lifetime of the putative 1-(3-nitrophenyl)ethyl carbocation intermediate of solvolysis (ca. 10-13 s-1) is too short to allow rearrangement that exchanges the positions of 16O and 18O at the sulfonate leaving group. This suggests that isomerization proceeds by a mechanism that avoids formation of the carbocation-anion pair intermediate.

UR - https://www.scopus.com/pages/publications/6444238093

U2 - 10.1021/ol0484409

DO - 10.1021/ol0484409

M3 - Article

C2 - 15387566

AN - SCOPUS:6444238093

SN - 1523-7060

VL - 6

SP - 3633

EP - 3636

JO - Organic Letters

JF - Organic Letters

IS - 20

ER -

Scrambling of oxygen-18 during the "Borderline" solvolysis of 1-(3-nitrophenyl)ethyl tosylate

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