Base- And Catalyst-Induced Orthogonal Site Selectivities in Acylation of Amphiphilic Diols

Natali Ashush; Reut Fallek; Amit Fallek; Roman Dobrovetsky; Moshe Portnoy

doi:https://doi.org/10.1021/acs.orglett.0c00830

Base- And Catalyst-Induced Orthogonal Site Selectivities in Acylation of Amphiphilic Diols

Natali Ashush, Reut Fallek, Amit Fallek, Roman Dobrovetsky, Moshe Portnoy

School of Chemistry

Tel Aviv University

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

Abstract

Seeking to selectively functionalize natural and synthetic amphiphiles, we explored acylation of model amphiphilic diols. The use of a nucleophilic catalyst enabled a remarkable shift of the site selectivity from the polar site, preferred in background noncatalyzed or base-promoted reactions, to the apolar site. This tendency was significantly enhanced for organocatalysts comprising an imidazole active site surrounded by long/branched tails. An explanation of these orthogonal modes of selectivity is supported by competitive experiments with monoalcohol substrates.

Original language	English
Pages (from-to)	3749-3754
Number of pages	6
Journal	Organic Letters
Volume	22
Issue number	10
DOIs	https://doi.org/10.1021/acs.orglett.0c00830
State	Published - 15 May 2020

All Science Journal Classification (ASJC) codes

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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https://doi.org/10.1021/acs.orglett.0c00830

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title = "Base- And Catalyst-Induced Orthogonal Site Selectivities in Acylation of Amphiphilic Diols",

abstract = "Seeking to selectively functionalize natural and synthetic amphiphiles, we explored acylation of model amphiphilic diols. The use of a nucleophilic catalyst enabled a remarkable shift of the site selectivity from the polar site, preferred in background noncatalyzed or base-promoted reactions, to the apolar site. This tendency was significantly enhanced for organocatalysts comprising an imidazole active site surrounded by long/branched tails. An explanation of these orthogonal modes of selectivity is supported by competitive experiments with monoalcohol substrates.",

author = "Natali Ashush and Reut Fallek and Amit Fallek and Roman Dobrovetsky and Moshe Portnoy",

note = "Funding Information: This research was supported by the Israel Science Foundation (Grant 955/10) and the United States–Israel Binational Science Foundation (BSF) (Grant 2012193). We thank Dr. Maria Kramer (Tel Aviv University) for assistance in the characterization of one of the intermediates.",

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T1 - Base- And Catalyst-Induced Orthogonal Site Selectivities in Acylation of Amphiphilic Diols

AU - Ashush, Natali

AU - Fallek, Reut

AU - Fallek, Amit

AU - Dobrovetsky, Roman

AU - Portnoy, Moshe

N1 - Funding Information: This research was supported by the Israel Science Foundation (Grant 955/10) and the United States–Israel Binational Science Foundation (BSF) (Grant 2012193). We thank Dr. Maria Kramer (Tel Aviv University) for assistance in the characterization of one of the intermediates.

PY - 2020/5/15

Y1 - 2020/5/15

N2 - Seeking to selectively functionalize natural and synthetic amphiphiles, we explored acylation of model amphiphilic diols. The use of a nucleophilic catalyst enabled a remarkable shift of the site selectivity from the polar site, preferred in background noncatalyzed or base-promoted reactions, to the apolar site. This tendency was significantly enhanced for organocatalysts comprising an imidazole active site surrounded by long/branched tails. An explanation of these orthogonal modes of selectivity is supported by competitive experiments with monoalcohol substrates.

AB - Seeking to selectively functionalize natural and synthetic amphiphiles, we explored acylation of model amphiphilic diols. The use of a nucleophilic catalyst enabled a remarkable shift of the site selectivity from the polar site, preferred in background noncatalyzed or base-promoted reactions, to the apolar site. This tendency was significantly enhanced for organocatalysts comprising an imidazole active site surrounded by long/branched tails. An explanation of these orthogonal modes of selectivity is supported by competitive experiments with monoalcohol substrates.

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M3 - مقالة

C2 - 32330055

SN - 1523-7060

VL - 22

SP - 3749

EP - 3754

JO - Organic Letters

JF - Organic Letters

IS - 10

ER -

Base- And Catalyst-Induced Orthogonal Site Selectivities in Acylation of Amphiphilic Diols

Abstract

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