H2020Индивидуална стипендия2020–2022

ALCO2-FUNC · A Remote-carboxylation Strategy for Alcohols via a Dual-catalytic System

„Хоризонт 2020“ — Действия „Мария Склодовска-Кюри“

Период: 2020-03-01 → 2022-02-28
Финансиране от ЕС: 160 932 €
Участници: 1
Схема: MSCA-IF-EF-ST

Линиите свързват координатора с партньорите.

Накратко на български

Методи за добавяне на въглероден диоксид към отдалечени части на алифатните алкохоли чрез двойна катализа се изследват за създаване на сложни молекули. Това помага за по-бързото производство на лекарства и превръща отпадъчния CO2 в полезни химикали.

Този кратък обзор е генериран от изкуствен интелект

Кратко обяснение, генерирано от езиков модел по текста на CORDIS. Оригиналът е по-долу.

Резултати накратко

A Remote-carboxylation Strategy for Alcohols via a Dual-catalytic System

The ability to introduce functionality into molecules in a regio- and chemoselective manner is of primary importance in the construction of high value molecular compounds, but still remains a major challenge for synthetic chemists. The utilization of functionalities present in readily available and inexpensive starting materials to direct the introduction of further complexity is an attractive strategy which has become increasingly popular. Despite recent advances, the remote functionalization of aliphatic alcohols still remains largely underdeveloped. Considering their prevalence in natural products, pharmaceuticals and chemical feedstocks, efforts to address this problem were deemed necessary. ALCO2-FUNC aimed to merge (reductive) nickel catalysis with photoredox catalysis to exploit advantages of both disciplines, enabling the development of a divergent strategy by careful control of key catalytic steps (Figure 1). Moreover, carbon dioxide was to be utilized as an abundant and economical C1 synthon to provide a valuable carboxylation strategy. See Figure 1 The development of mild and green synthetic procedures to quickly and selectively produce active pharmaceutical agents is of great importance for global health as it streamlines the discovery and production processes, resulting in less time to market and to benefit those in need. In addition, the application of carbon dioxide is also relevant, as it contributes to the circular economy concept, where waste CO2 streams can be used to produce value-added chemicals. The main objective of ALCO2-FUNC was to develop site-selective, catalytic C–C bond-formation of abundant aliphatic alcohols at distal sp3 C–H sites, thus turning simplicity into complexity for accessing valuable products from simple precursors. The specific objectives were the following: 1. To implement a β-carboxylation of alcohols with CO2 via dual photoredox/ nickel-catalysis. 2. To enable a remote-carboxylation of aliphatic alcohols with CO2 at distal sp3 C–H sites via a chain-walking scenario. 3. To perform electrochemical and mechanistic study on key Ni-alkyl species.

Текст от CORDIS, на английски · Данни: CORDIS, © Европейски съюз

Цел на проекта

The ability to introduce functionality into molecules in a regio- and chemoselective selective manner is of primary importance in the construction of high value molecular compounds but still remains a major challenge for synthetic chemists. The utilization of functionalities present in readily available and inexpensive starting materials to direct the introduction of further complexity is an attractive strategy which has become increasingly popular. Despite recent advances, the remote-functionalization of aliphatic alcohols still remains largely underdeveloped. Considering their prevalence in natural products, compounds displaying important biological activities and chemical feedstocks, efforts to address this problem are deemed necessary. ALCO2-FUNC will make use of an easily installed α bromo-silyl tether to direct functionalization at neighbouring sites. The tether will partake in single electron transfer with a suitable nickel catalyst, initiating a directed radical rebound cascade. The merger of (reductive) nickel catalysis with photoredox catalysis will exploit advantages of both disciplines, enabling the development of a divergent strategy by careful control of key catalytic steps. Furthermore, carbon dioxide will be utilized as a C1 synthon to provide a valuable carboxylation strategy. To such end, simple alcohols will be converted to their β-carboxylated counterparts (via regioselective 1,5 hydrogen atom transfer) or remotely-carboxylated (following a nickel chain-walking sequence). Taken together, the synergy between photoredox and nickel catalysis will be employed in ALCO2-FUNC to develop novel synthetic strategies to access high value compounds from simple precursors. The proposed methodology is expected to operate under mild conditions (room temperature, low-energy irradiation) increasing functional group compatibility and setting the basis for the implementation in the late-stage functionalization of advanced pharmaceuticals.

Оригинален текст от CORDIS (на английски).

Участници

FUNDACIO INSTITUT CATALA D'INVESTIGACIO QUIMICA · TARRAGONAКоординаторИспания