One and Two-Carbon Homologation of Primary and Secondary Alcohols to Corresponding Carboxylic Esters Using β-Carbonyl BT Sulfones as a Common Intermediate

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389030%3A_____%2F18%3A00489842" target="_blank" >RIV/61389030:_____/18:00489842 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61989592:15110/18:73591141 RIV/61989592:15310/18:73591141

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.joc.8b00112" target="_blank" >http://dx.doi.org/10.1021/acs.joc.8b00112</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.joc.8b00112" target="_blank" >10.1021/acs.joc.8b00112</a>

Jazyk výsledku

angličtina

Název v původním jazyce

One and Two-Carbon Homologation of Primary and Secondary Alcohols to Corresponding Carboxylic Esters Using β-Carbonyl BT Sulfones as a Common Intermediate

Popis výsledku v původním jazyce

Herein we report the efficient one- and two-carbon homologation of 1° and 2° alcohols to their corresponding homologated esters via the Mitsunobu reaction using β-carbonyl benzothiazole (BT) sulfone intermediates. The one-carbon homologation approach uses standard Mitsunobu C-S bond formation, oxidation and subsequent alkylation, while the two-carbon homologation uses a less common C-C bond forming Mitsunobu reaction. In this latter case, the use of β-BT sulfone bearing esters lowers the pK a sufficiently enough for the substrate to be used as a carbon-based nucleophile and deliver the homologated β-BT sulfone ester, and this superfluous sulfone group can then be cleaved. In this paper we describe several methods for the effective desulfonylation of BT sulfones and have developed methodology for one-pot alkylation-desulfonylation sequences. As such, overall, a one-carbon homologation sequence can be achieved in a two-pot (four step) procedure and the two-carbon homologation in a two-pot (three step) procedure (three-pot, four step when C-acid synthesis is included). This methodology has been applied to a wide variety of functionality (esters, silyl ethers, benzyls, heteroaryls, ketones, olefins and alkynes) and are all tolerated well providing good to very good overall yields. The power of our method was demonstrated in site-selective ingenol C20 allylic alcohol two-carbon homologation.

Název v anglickém jazyce

One and Two-Carbon Homologation of Primary and Secondary Alcohols to Corresponding Carboxylic Esters Using β-Carbonyl BT Sulfones as a Common Intermediate

Popis výsledku anglicky

Herein we report the efficient one- and two-carbon homologation of 1° and 2° alcohols to their corresponding homologated esters via the Mitsunobu reaction using β-carbonyl benzothiazole (BT) sulfone intermediates. The one-carbon homologation approach uses standard Mitsunobu C-S bond formation, oxidation and subsequent alkylation, while the two-carbon homologation uses a less common C-C bond forming Mitsunobu reaction. In this latter case, the use of β-BT sulfone bearing esters lowers the pK a sufficiently enough for the substrate to be used as a carbon-based nucleophile and deliver the homologated β-BT sulfone ester, and this superfluous sulfone group can then be cleaved. In this paper we describe several methods for the effective desulfonylation of BT sulfones and have developed methodology for one-pot alkylation-desulfonylation sequences. As such, overall, a one-carbon homologation sequence can be achieved in a two-pot (four step) procedure and the two-carbon homologation in a two-pot (three step) procedure (three-pot, four step when C-acid synthesis is included). This methodology has been applied to a wide variety of functionality (esters, silyl ethers, benzyls, heteroaryls, ketones, olefins and alkynes) and are all tolerated well providing good to very good overall yields. The power of our method was demonstrated in site-selective ingenol C20 allylic alcohol two-carbon homologation.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

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

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Journal of Organic Chemistry

ISSN

0022-3263

e-ISSN

—

Svazek periodika

83

Číslo periodika v rámci svazku

9

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

4990-5001

Kód UT WoS článku

000431726800009

EID výsledku v databázi Scopus

2-s2.0-85046624051