Reasons Why Aldehydes Do Not Generally Participate in
Cucurbit[n]uril Forming Reactions

J 2010

Reasons Why Aldehydes Do Not Generally Participate in Cucurbit[n]uril Forming Reactions

MA, Da, Zuzana GARGULÁKOVÁ, Peter Y. ZAVALIJT, Vladimír ŠINDELÁŘ, Lyle ISAACS et. al.

Základní údaje

Originální název

Reasons Why Aldehydes Do Not Generally Participate in Cucurbit[n]uril Forming Reactions

Název česky

Důvody, proč se aldehydy obecně nezúčastňují reakcí poskytujících cucurbit[n]urily

Autoři

MA, Da (840 Spojené státy), Zuzana GARGULÁKOVÁ (203 Česká republika, domácí), Peter Y. ZAVALIJT (840 Spojené státy), Vladimír ŠINDELÁŘ (203 Česká republika, garant, domácí) a Lyle ISAACS (840 Spojené státy)

Vydání

Journal of Organic Chemistry, 2010, 0022-3263

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10401 Organic chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 4.002

Kód RIV

RIV/00216224:14310/10:00048650

Organizační jednotka

Přírodovědecká fakulta

UT WoS

000277274000018

Klíčová slova česky

cucurbiturily; macrocykly

Klíčová slova anglicky

cucurbiturils; macrocycles

Změněno: 12. 12. 2011 13:24, prof. Ing. Vladimír Šindelář, Ph.D.

Anotace

ORIG CZ

V originále

The reaction of substituted glycolurils or a glycoluril dimer with a dialdehyde (o_phthalaldehyde) delivers S_shaped dimers and an S-shaped tetramer selectively. A combination of X_ray crystallography, PM3 calculations, and product resubmission experiments establish that the S_shaped isomers are thermodynamically more stable than the C_shaped diastereomers which we attribute to the conformational preferences of the newly formed benzo bicyclo[3.3.2]decane ring system. The preferential formation of S_shaped subunits is one reason why o_phthalaldehyde and possibly other aldehydes do not usually participate in CB[n] forming reactions. We also present evidence that points toward an equilibrium between glycoluril monomer + phthalaldehyde and S_shaped dimer + water that responds to concentration over the 1_50 mM range. This result suggests a second reason, insufficient reactivity (e.g., low equilibrium constant), why o-phthalaldehyde and possibly other aldehydes do not participate in CB[n] forming reactions. Delineation of the reasons why some aldehydes fail in these reactions is the first step toward devising methods to overcome these limitations.

Česky

Byly popsány reakce mezi glykolurily a o_ftalalehydem, které vedli k přípravě dimerů.

Návaznosti

GP203/07/P382, projekt VaV

Název: Nové deriváty cucurbit[n]urilu

Investor: Grantová agentura ČR, Nové deriváty cucurbit[n]urilu

Citovat

MA, Da, Zuzana GARGULÁKOVÁ, Peter Y. ZAVALIJT, Vladimír ŠINDELÁŘ a Lyle ISAACS. Reasons Why Aldehydes Do Not Generally Participate in Cucurbit[n]uril Forming Reactions. Journal of Organic Chemistry. 2010, roč. 75, č. 9, s. 2934-2941, 13 s. ISSN 0022-3263.

@article{883648,
   author = {Ma, Da and Garguláková, Zuzana and Zavalijt, Peter Y. and Šindelář, Vladimír and Isaacs, Lyle},
   article_number = {9},
   keywords = {cucurbiturils; macrocycles},
   language = {eng},
   issn = {0022-3263},
   journal = {Journal of Organic Chemistry},
   title = {Reasons Why Aldehydes Do Not Generally Participate in Cucurbit[n]uril Forming Reactions},
   url = {http://pubs.acs.org/doi/abs/10.1021/jo100186q},
   volume = {75},
   year = {2010}
}

TY  - JOUR
ID  - 883648
AU  - Ma, Da - Garguláková, Zuzana - Zavalijt, Peter Y. - Šindelář, Vladimír - Isaacs, Lyle
PY  - 2010
TI  - Reasons Why Aldehydes Do Not Generally Participate in Cucurbit[n]uril Forming Reactions
JF  - Journal of Organic Chemistry
VL  - 75
IS  - 9
SP  - 2934-2941
EP  - 2934-2941
SN  - 00223263
KW  - cucurbiturils
KW  - macrocycles
UR  - http://pubs.acs.org/doi/abs/10.1021/jo100186q
N2  - The reaction of substituted glycolurils or a glycoluril dimer with a dialdehyde (o_phthalaldehyde) delivers S_shaped dimers and an S-shaped tetramer selectively. A combination of X_ray crystallography, PM3 calculations, and product resubmission experiments establish that the S_shaped isomers are thermodynamically more stable than the C_shaped diastereomers which we attribute to the conformational preferences of the newly formed benzo bicyclo[3.3.2]decane ring system. The preferential formation of S_shaped subunits is one reason why o_phthalaldehyde and possibly other aldehydes do not usually participate in CB[n] forming reactions. We also present evidence that points toward an equilibrium between glycoluril monomer + phthalaldehyde and S_shaped dimer + water that responds to concentration over the 1_50 mM range. This result suggests a second reason, insufficient reactivity (e.g., low equilibrium constant), why o-phthalaldehyde and possibly other aldehydes do not participate in CB[n] forming reactions. Delineation of the reasons why some aldehydes fail in these reactions is the first step toward devising methods to overcome these limitations.
ER  -

MA, Da, Zuzana GARGULÁKOVÁ, Peter Y. ZAVALIJT, Vladimír ŠINDELÁŘ a Lyle ISAACS. Reasons Why Aldehydes Do Not Generally Participate in Cucurbit[n]uril Forming Reactions. \textit{Journal of Organic Chemistry}. 2010, roč.~75, č.~9, s.~2934-2941, 13 s. ISSN~0022-3263.

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