Unique Stereocontrol in Carborane Chemistry: Skeletal Alkylcarbonation (SAC) versus Exoskeletal Alkylmethylation (EAM) Reactions

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F15%3A39900093" target="_blank" >RIV/00216275:25310/15:39900093 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388980:_____/15:00443607

Výsledek na webu

<a href="http://dx.doi.org/10.1002/anie.201500824" target="_blank" >http://dx.doi.org/10.1002/anie.201500824</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/anie.201500824" target="_blank" >10.1002/anie.201500824</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Unique Stereocontrol in Carborane Chemistry: Skeletal Alkylcarbonation (SAC) versus Exoskeletal Alkylmethylation (EAM) Reactions

Popis výsledku v původním jazyce

Reactions between the arachno-6,9-C2B8H14 (1) dicarbaborane and acyl chlorides, RCOCl (2), are subject to stereocontrol that completely changes the nature of the reaction products. While most chlorides produce the 8-R-nido-7,8,9-C3B8H11 (3) tricarbollides (by skeletal alkylcarbonation=SAC), bulky RCOCls (2; where R=1-adamantyl, 2a; 1-mesityl, 2b; 9-anthranyl, 2c; 1-naphthyl, 2d) in 1,2-dichloroethane (DCE) in the presence of triethylamine at 40-60 degrees C gave a series of entirely different 1-R-2-CH3-closo-1,6-C2B8H8 (4) dicarbaboranes upon acidification with conc. H2SO4 (by exosleletal alkylmehylation=EAM). Both types of reactions seem to proceed via a common [8-R-nido-7,8,9-C3B8H10](-) (3(-)) anion which in the EAM case is unstable because of steric crowd and undergoes rearrangement via the isomeric [R-nido-7,8,10-C3B8H10](-) tricarbollide structures which, on protonation, undergo reductive extraction of one CH vertex to generate the 2-CH3 substituent in structure 4.

Název v anglickém jazyce

Unique Stereocontrol in Carborane Chemistry: Skeletal Alkylcarbonation (SAC) versus Exoskeletal Alkylmethylation (EAM) Reactions

Popis výsledku anglicky

Reactions between the arachno-6,9-C2B8H14 (1) dicarbaborane and acyl chlorides, RCOCl (2), are subject to stereocontrol that completely changes the nature of the reaction products. While most chlorides produce the 8-R-nido-7,8,9-C3B8H11 (3) tricarbollides (by skeletal alkylcarbonation=SAC), bulky RCOCls (2; where R=1-adamantyl, 2a; 1-mesityl, 2b; 9-anthranyl, 2c; 1-naphthyl, 2d) in 1,2-dichloroethane (DCE) in the presence of triethylamine at 40-60 degrees C gave a series of entirely different 1-R-2-CH3-closo-1,6-C2B8H8 (4) dicarbaboranes upon acidification with conc. H2SO4 (by exosleletal alkylmehylation=EAM). Both types of reactions seem to proceed via a common [8-R-nido-7,8,9-C3B8H10](-) (3(-)) anion which in the EAM case is unstable because of steric crowd and undergoes rearrangement via the isomeric [R-nido-7,8,10-C3B8H10](-) tricarbollide structures which, on protonation, undergo reductive extraction of one CH vertex to generate the 2-CH3 substituent in structure 4.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CA - Anorganická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/GAP207%2F11%2F0705" target="_blank" >GAP207/11/0705: Arenové komplexy železa modikované karborany</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2015

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Angewandte Chemie (International Edition)

ISSN

1433-7851

e-ISSN

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Svazek periodika

54

Číslo periodika v rámci svazku

16

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

4

Strana od-do

4937-4940

Kód UT WoS článku

000352622400047

EID výsledku v databázi Scopus

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