Novel chemistry of alpha-tosyloxy ketones: applications to the solution- and solid-phase synthesis of privileged heterocycle and enediyne libraries

Research output: Contribution to journal › Journal article › Research › peer-review

Standard

Novel chemistry of alpha-tosyloxy ketones: applications to the solution- and solid-phase synthesis of privileged heterocycle and enediyne libraries. / Nicolaou, K C; Montagnon, T; Ulven, T; Baran, P S; Zhong, Y-L; Sarabia, F.

In: American Chemical Society. Journal, Vol. 124, No. 20, 22.05.2002, p. 5718-5728.

Research output: Contribution to journal › Journal article › Research › peer-review

Harvard

Nicolaou, KC, Montagnon, T, Ulven, T, Baran, PS, Zhong, Y-L & Sarabia, F 2002, 'Novel chemistry of alpha-tosyloxy ketones: applications to the solution- and solid-phase synthesis of privileged heterocycle and enediyne libraries', American Chemical Society. Journal, vol. 124, no. 20, pp. 5718-5728.

APA

Nicolaou, K. C., Montagnon, T., Ulven, T., Baran, P. S., Zhong, Y-L., & Sarabia, F. (2002). Novel chemistry of alpha-tosyloxy ketones: applications to the solution- and solid-phase synthesis of privileged heterocycle and enediyne libraries. American Chemical Society. Journal, 124(20), 5718-5728.

Vancouver

Nicolaou KC, Montagnon T, Ulven T, Baran PS, Zhong Y-L, Sarabia F. Novel chemistry of alpha-tosyloxy ketones: applications to the solution- and solid-phase synthesis of privileged heterocycle and enediyne libraries. American Chemical Society. Journal. 2002 May 22;124(20):5718-5728.

Author

Nicolaou, K C ; Montagnon, T ; Ulven, T ; Baran, P S ; Zhong, Y-L ; Sarabia, F. / Novel chemistry of alpha-tosyloxy ketones: applications to the solution- and solid-phase synthesis of privileged heterocycle and enediyne libraries. In: American Chemical Society. Journal. 2002 ; Vol. 124, No. 20. pp. 5718-5728.

Bibtex

@article{6b3d4e802c744bdd808532474ebf9139,
title = "Novel chemistry of alpha-tosyloxy ketones: applications to the solution- and solid-phase synthesis of privileged heterocycle and enediyne libraries",
abstract = "New synthetic technologies for the preparation and elaboration of alpha-tosyloxy ketones in solution- and on solid-phase are described. Both olefins and ketones serve as precursors to these relatively stable chemical entities: olefins via a novel one-pot epoxidation, arylsulfonic acid displacement, and oxidation sequence, and ketones by direct exposure to arylsulfonic acids in the presence of diacetoxy iodobenzene. Reaction of these substrates with O-, S-, or N-centered nucleophiles leads to incorporation of the nucleophile with concomitant expulsion of the sulfonate, while exposure to bis-functional nucleophiles furnishes annulated heterocyclic systems. In addition, the reactions of carbon-centered nucleophiles with alpha-tosylyloxy ketones are also explored. The collated data for all these nucleophiles provide compelling evidence for the proposal that different reaction pathways are followed when alpha-tosyloxy ketones are engaged by {"}hard{"} versus {"}soft{"} nucleophiles. The accessibility and site-selectivity of the chemistry demonstrated herein offer the promise of an expanded use for this moiety in solid-phase library construction, in particular, and in the field of organic synthesis, in general.",
keywords = "Alkynes, Heterocyclic Compounds, Ketones, Tosyl Compounds",
author = "Nicolaou, {K C} and T Montagnon and T Ulven and Baran, {P S} and Y-L Zhong and F Sarabia",
year = "2002",
month = may,
day = "22",
language = "English",
volume = "124",
pages = "5718--5728",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "ACS Publications",
number = "20",

}

RIS

TY - JOUR

T1 - Novel chemistry of alpha-tosyloxy ketones: applications to the solution- and solid-phase synthesis of privileged heterocycle and enediyne libraries

AU - Nicolaou, K C

AU - Montagnon, T

AU - Ulven, T

AU - Baran, P S

AU - Zhong, Y-L

AU - Sarabia, F

PY - 2002/5/22

Y1 - 2002/5/22

N2 - New synthetic technologies for the preparation and elaboration of alpha-tosyloxy ketones in solution- and on solid-phase are described. Both olefins and ketones serve as precursors to these relatively stable chemical entities: olefins via a novel one-pot epoxidation, arylsulfonic acid displacement, and oxidation sequence, and ketones by direct exposure to arylsulfonic acids in the presence of diacetoxy iodobenzene. Reaction of these substrates with O-, S-, or N-centered nucleophiles leads to incorporation of the nucleophile with concomitant expulsion of the sulfonate, while exposure to bis-functional nucleophiles furnishes annulated heterocyclic systems. In addition, the reactions of carbon-centered nucleophiles with alpha-tosylyloxy ketones are also explored. The collated data for all these nucleophiles provide compelling evidence for the proposal that different reaction pathways are followed when alpha-tosyloxy ketones are engaged by "hard" versus "soft" nucleophiles. The accessibility and site-selectivity of the chemistry demonstrated herein offer the promise of an expanded use for this moiety in solid-phase library construction, in particular, and in the field of organic synthesis, in general.

AB - New synthetic technologies for the preparation and elaboration of alpha-tosyloxy ketones in solution- and on solid-phase are described. Both olefins and ketones serve as precursors to these relatively stable chemical entities: olefins via a novel one-pot epoxidation, arylsulfonic acid displacement, and oxidation sequence, and ketones by direct exposure to arylsulfonic acids in the presence of diacetoxy iodobenzene. Reaction of these substrates with O-, S-, or N-centered nucleophiles leads to incorporation of the nucleophile with concomitant expulsion of the sulfonate, while exposure to bis-functional nucleophiles furnishes annulated heterocyclic systems. In addition, the reactions of carbon-centered nucleophiles with alpha-tosylyloxy ketones are also explored. The collated data for all these nucleophiles provide compelling evidence for the proposal that different reaction pathways are followed when alpha-tosyloxy ketones are engaged by "hard" versus "soft" nucleophiles. The accessibility and site-selectivity of the chemistry demonstrated herein offer the promise of an expanded use for this moiety in solid-phase library construction, in particular, and in the field of organic synthesis, in general.

KW - Alkynes

KW - Heterocyclic Compounds

KW - Ketones

KW - Tosyl Compounds

M3 - Journal article

VL - 124

SP - 5718

EP - 5728

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 20

ER -

ID: 189160785