A Neutral PC_NHCP Co(I)–Me Pincer Complex as a Catalyst for N-Allylic Isomerization with a Broad Substrate Scope

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(7), С. 4319 - 4325

Опубликована: Март 23, 2024

Earth-abundant-metal catalyzed double bond transposition offers a sustainable and atom-economical route toward the synthesis of internal alkenes. With an emphasis specifically on olefins ethers, isomerization allylic amines has been particularly under represented in literature. Herein, we report efficient methodology for selective N-allylic organic compounds, including amines, amides, imines. The reaction is by neutral PCNHCP cobalt(I) pincer complex proceeds via π-allyl mechanism. occurs readily at 80–90 °C, it compatible with wide variety functional groups. situ formed enamines could additionally be used one-pot inverse-electron-demand Diels–Alder to furnish series diversely substituted heterobiaryls, which further discussed this report.

Язык: Английский

---

Molecular insights into chirality transfer from double axially chiral phosphoric acid in a synergistic enantioselective intramolecular amination

Chemical Science, Год журнала: 2021, Номер 13(5), С. 1323 - 1334

Опубликована: Дек. 29, 2021

In the most general practice of asymmetric catalysis, a chiral catalyst, typically bearing center or an axis chirality, is employed as source for imparting enantiocontrol over developing product. Given current interest toward optically pure compounds, various forms induction enabled by diverse sources well use multiple catalysts under one-pot conditions have been in focus. one such promising development, achiral N-sulfonamide protected 1,6-amino allyl alcohol (NaphSO2NHCH2C(Ph)2CH2CH[double bond, length m-dash]CHCH2OH) was subjected to Tsuji-Trost activation and intramolecular amination form important pyrrolidine frameworks. A dual catalytic system comprising Pd(PPh3)4 DAPCy (β-cyclohexyl substituted double axially phosphoric acid derived from two homocoupled BINOL backbones with dynamic central axis) mild reported offer quantitative conversion ee 95%. Here, we provide molecular insights into origin DAPCy, obtained through comprehensive density functional theory (SMD(toluene)/B3LYP-D3/6-31G**,Pd(SDD)) investigation. Two key steps mechanism are identified involve cooperative mode Pd-bound Pd-π-allyl moiety at end substrate, followed nucleophilic addition other yield derivative α-vinyl stereogenic center. (S,R,S)-DAPCy found steer dehydroxylation intermediate suitably poised si prochiral face addition. enantiocontrolled (as turn-over determining step) addition, catalyst serve phosphate counterion. The facilitated series N-H⋯O, C-H⋯O, C-H⋯π, lone pair (lp)⋯π, O-H⋯O, O-H⋯π, π⋯π noncovalent interactions, which noted more effective lower energy C-N bond formation transition state moiety. These novel could be valuable exploiting modes stereoinduction.

Язык: Английский

---

Chiral trifluoromethylated enamides: Synthesis and applications

Chem Catalysis, Год журнала: 2023, Номер 3(12), С. 100813 - 100813

Опубликована: Ноя. 14, 2023

Enamides are versatile building blocks in organic synthesis that give access to complex nitrogen-containing compounds. However, despite the interest these compounds, synthetic strategies enamides with carbon-centered chirality atre scarce. In this work, we report an efficient method for of a new class chiral trifluoromethylated stereogenic center from easily accessible allylic amines by effective chirality-transfer process. The gives excellent yields and diastereo- enantioselectivities. scope reaction is broad, various substituents functional groups tolerated. Furthermore, transformations were carried out trifluoromethylated, structures. For example, photocatalytic E/Z isomerization also presented.

Язык: Английский

---

A Neutral PCNHCP Co(I)-Me Pincer Complex as a Universal Catalyst for N-Allylic Isomerization

Опубликована: Ноя. 16, 2023

Earth-abundant metal catalyzed double bond transposition offers a sustainable and atom economical route towards the synthesis of internal alkenes. With emphasis specifically on olefins ethers, isomerization allylic amines has been particularly underrepresented in literature. Herein, we report an efficient methodology for selective N-allylic organic compounds including, amines, amides, imines. The reaction is by neutral PCNHCP Cobalt(I) pincer complex proceeds via π-allyl mechanism that includes unusual 1,2-methyl migration. occurs readily at 80 °C it compatible with wide variety functional groups. in-situ formed enamines, could additionally be used one-pot inverse-electron-demand Diels-Alder to furnish series diversely substituted hetero-biaryls, which further discussed this report.

Язык: Английский

---

Stereoselective Synthesis of 2‐Oxyenamides**

European Journal of Organic Chemistry, Год журнала: 2022, Номер 2022(31)

Опубликована: Июль 18, 2022

Abstract An improved route for the highly stereoselective synthesis of ( Z )‐2‐oxyenamides is reported. The desired products can be accessed in only three steps from aminoacetaldehyde dimethyl acetal as common, readily available building block a modular fashion. procedure has been applied to various acylated and sufonylated oxyenamides. Mechanistic theoretical studies provide conclusive rationale observed stereoselectivities.

Язык: Английский

---