Facile and Highly Diastereoselective Synthesis of syn- and cis-1,2-Diol Derivatives from Protected -Hydroxy Ketones

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F15%3A10316608" target="_blank" >RIV/00216208:11310/15:10316608 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1002/ejoc.201501174" target="_blank" >http://dx.doi.org/10.1002/ejoc.201501174</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/ejoc.201501174" target="_blank" >10.1002/ejoc.201501174</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Facile and Highly Diastereoselective Synthesis of syn- and cis-1,2-Diol Derivatives from Protected -Hydroxy Ketones

Popis výsledku v původním jazyce

An efficient method for the synthesis of monoprotected syn- or cis-1,2-diol derivatives by reduction of easily accessible -(2,2,6,6-tetramethylpiperidinyloxy) ketones is reported. The -(tetramethylpiperidinyloxy) group as the stereodirecting group induces in unhindered acyclic or cyclic ketones complete syn- or cis-diastereoselectivity, respectively, with L-Selectride. For more hindered derivatives, where L-Selectride becomes unreactive, LiAlH4 proved effective, essentially showing the same high selectivity. The diastereoselectivity of the reduction can be rationalized for acyclic ketones by the Felkin-Anh model, whereas for cyclic substrates, attack from the face opposite to the tetramethylpiperidinyloxy group predictably prevails with high selectivity regardless of the substitution pattern. The liberation of free diols was achieved by reductive N-O bond cleavage of the alkoxyamine unit.

Název v anglickém jazyce

Facile and Highly Diastereoselective Synthesis of syn- and cis-1,2-Diol Derivatives from Protected -Hydroxy Ketones

Popis výsledku anglicky

An efficient method for the synthesis of monoprotected syn- or cis-1,2-diol derivatives by reduction of easily accessible -(2,2,6,6-tetramethylpiperidinyloxy) ketones is reported. The -(tetramethylpiperidinyloxy) group as the stereodirecting group induces in unhindered acyclic or cyclic ketones complete syn- or cis-diastereoselectivity, respectively, with L-Selectride. For more hindered derivatives, where L-Selectride becomes unreactive, LiAlH4 proved effective, essentially showing the same high selectivity. The diastereoselectivity of the reduction can be rationalized for acyclic ketones by the Felkin-Anh model, whereas for cyclic substrates, attack from the face opposite to the tetramethylpiperidinyloxy group predictably prevails with high selectivity regardless of the substitution pattern. The liberation of free diols was achieved by reductive N-O bond cleavage of the alkoxyamine unit.

Druh

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

CEP obor

CC - Organická chemie

OECD FORD obor

—

Projekt

—

Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2015

Kód důvěrnosti údajů

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

Název periodika

European Journal of Organic Chemistry

ISSN

1434-193X

e-ISSN

—

Svazek periodika

neuveden

Číslo periodika v rámci svazku

35

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

14

Strana od-do

7785-7798

Kód UT WoS článku

000366426600019

EID výsledku v databázi Scopus

2-s2.0-84948798902