Difunctionalization Processes Enabled by Hexafluoroisopropanol

ACS Organic & Inorganic Au, Год журнала: 2024, Номер 4(3), С. 287 - 300

Опубликована: Март 4, 2024

In the past 5 years, hexafluoroisopropanol (HFIP) has been used as a unique solvent or additive to enable challenging transformations through substrate activation and stabilization of reactive intermediates. this Review, we aim at describing difunctionalization processes which were unlocked when HFIP was involved. Specifically, focus on cyclizations additions alkenes, alkynes, epoxides, carbonyls that introduce wide range functional groups interest.

Язык: Английский

---

Catalytic Synthesis of β‐(Hetero)arylethylamines: Modern Strategies and Advances

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(41)

Опубликована: Авг. 21, 2023

Abstract β‐(Hetero)arylethylamines appear in a myriad of pharmaceuticals due to their broad spectrum biological properties, making them prime candidates for drug discovery. Conventional methods preparation often require engineered substrates that limit the flexibility synthetic routes and diversity compounds can be accessed. Consequently, provide rapid versatile access those scaffolds remain limited. To overcome these challenges, chemists have designed innovative modular strategies β‐(hetero)arylethylamine motif, paving way more extensive use future pharmaceuticals. This review outlines recent progresses synthesis (hetero)arylethylamines emphasizes how innovations enabled new levels molecular complexity, selectivity, practicality.

Язык: Английский

---

Stereoselective synthesis of tetra- and tri-substituted alkenyl nitriles via aminative ring-opening of cyclopropenes with iron-aminyl radical

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 3, 2025

Язык: Английский

---

Strategies for Direct, Transition Metal‐Free Addition of Nitrogen Synthons to Alkenes

Helvetica Chimica Acta, Год журнала: 2023, Номер 107(1)

Опубликована: Дек. 15, 2023

Abstract The incorporation of nitrogen into small molecules is one the highest‐demanded transformations in modern synthetic chemistry. Alkene difunctionalization and aziridination offer desirable approaches to these amino synthons from feedstock precursors. Although groups can be added alkenes following alkene reaction with an initiation reagent, most approach involves direct addition group alkene, allowing for a range possible secondary functionalization outcomes. many strategies have been accomplished through use transition metals, utility metal‐free still at forefront chemistry, both development demand. This review aims present comprehensive history current state‐of‐the‐art metal‐free, alkenes.

Язык: Английский

---

Stereospecific Aminative Cyclizations Triggered by Intermolecular Aza‐Prilezhaev Alkene Aziridination

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(48)

Опубликована: Окт. 17, 2023

Under acidic reaction conditions (TFA), deprotection of BocNR(OSO2 R) reagents triggers intermolecular aminative cyclizations alkenes equipped with pendant nucleophiles. The processes are predicated on a sequence stereospecific aza-Prilezhaev aziridination followed by SN 2-like opening the nucleophile. method offers broad scope respect to nucleophile (N-, O- or C-based), alkene and cyclization mode, allowing installation two contiguous stereocenters under operationally simple conditions.

Язык: Английский

---

Transition-metal-free and additive-free intermolecular hydroarylation of alkenes with indoles in hexafluoroisopropanol

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(48), С. 9534 - 9541

Опубликована: Янв. 1, 2023

Hydroarylation of alkenes with indoles in hexafluoroisopropanol (HFIP) without the presence any transition metals or additives.

Язык: Английский

---

Iron(II)‐Catalyzed 1,2‐Diamination of Styrenes Installing a Terminal NH2 Group Alongside Unprotected Amines

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(45)

Опубликована: Июль 17, 2024

1,2-Diamination of alkenes represents an attractive way to generate differentiated vicinal diamines, which are prevalent motifs in biologically active compounds and catalysts. However, existing methods usually limited scope produce diamines where one or both nitrogens protected, adding synthetic steps for deprotection further N-functionalization reach a desired target. Furthermore, the range amino groups that can be introduced at internal position is fairly limited. Here we describe 1,2-diamination styrenes directly installs free group terminal wide variety unprotected nitrogen nucleophiles (primary secondary alkyl aromatic amines, sulfoximines, N-heterocycles, ammonia surrogate) position. Two complementary sets conditions encompass electronically activated deactivated with diverse substitution patterns functional groups. Moreover, this strategy extended 1,2-aminothiolation styrenes.

Язык: Английский

---

An Aza‐Prilezhaev‐Based Method Inverts Regioselectivity in Stereospecific Alkene 1,2‐Aminohydroxylations

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(49)

Опубликована: Авг. 22, 2024

Abstract Under acidic conditions (TFA) and in the presence of water, BocNHOTs promotes stereospecific 1,2‐aminohydroxylations alkenes. The processes involve intermolecular aza‐Prilezhaev aziridination followed by S N 2 opening water. This reagent combination provides regiochemical outcomes that are opposite to, or more selective than those observed using epoxidation initiated 1,2‐aminohydroxylation protocols. Replacement water other nucleophiles allows 1,2‐amino(thio)etherification, diamination, aminoazidation aminofluorination reactions. Intramolecular also feasible, including unusual variants evoke azabicyclobutane‐like reactivity.

Язык: Английский

---

Synthesis of Phenethylamine‐Azulene Conjugates Enabled by Regioselective Ring Opening of Aziridines

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 366(4), С. 1007 - 1012

Опубликована: Ноя. 21, 2023

Abstract The BF 3 ⋅OEt 2 ‐catalyzed reaction of azulene with N ‐protected aziridines represents a general, efficient (up to 91% yield) and regioselective approach phenethylamine‐azulene conjugates. Stereochemical studies DFT calculations lend support concerted S 2‐type mechanism governing the ring‐opening aziridine.

Язык: Английский

---

Catalytic Synthesis of β‐(Hetero)arylethylamines: Modern Strategies and Advances

Angewandte Chemie, Год журнала: 2023, Номер 135(41)

Опубликована: Авг. 21, 2023

Abstract β‐(Hetero)arylethylamines appear in a myriad of pharmaceuticals due to their broad spectrum biological properties, making them prime candidates for drug discovery. Conventional methods preparation often require engineered substrates that limit the flexibility synthetic routes and diversity compounds can be accessed. Consequently, provide rapid versatile access those scaffolds remain limited. To overcome these challenges, chemists have designed innovative modular strategies β‐(hetero)arylethylamine motif, paving way more extensive use future pharmaceuticals. This review outlines recent progresses synthesis (hetero)arylethylamines emphasizes how innovations enabled new levels molecular complexity, selectivity, practicality.

Язык: Английский

---