Direct Catalytic Asymmetric and Regiodivergent N1‐ and C3‐Allenylic Alkylation of Indoles

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(21)

Опубликована: Март 21, 2023

Herein we report a Pd-catalyzed asymmetric allenylic alkylation strategy for the direct functionalization of 1H-indoles by employing P-chiral BIBOP-type ligands. The regioselectivity (N1/C3) this process can be switched efficiently. Using Cs2 CO3 at elevated temperatures in MeCN, N1-alkylated indoles bearing axial chirality with stereocenter non-adjacent (β) to nitrogen are produced good yields high enantioselectivity and complete N1-regioselectivity regardless electronic properties substitution patterns diverse indoles. K2 room temperature CH2 Cl2 , chiral C3-alkylated also obtained. Notably, introduce new class tri-substituted electrophiles that proceeded through different pathways from di-substituted electrophiles.

Язык: Английский

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Transition‐Metal‐Catalyzed Transformations Involving the Heck Reaction

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(15), С. 2436 - 2466

Опубликована: Июнь 12, 2023

Abstract Elaborated molecular architectures including complex carbocycles, heterocycles, and polycyclic structures represent an important class of organic compounds because they are ubiquitous structural units in a broad variety biologically pharmacologically relevant natural products, medicinal molecules, functional materials. A major challenge modern synthetic methodology is the development strategically efficient selective construction these from readily available starting Transition‐metal‐catalyzed transformations involving Heck reaction as pivotal step have afforded powerful approach for accessing sophisticated skeletons set easy‐to handle materials, thus highlighting its potential significance streamlining drug discovery process. Over past few decades, significant effort has been devoted to derivatives versatile routes, number direct strategies reported. In this review, latest advances transition‐metal‐catalyzed critical summarized, which could be divided into six categories: 1) Heck/Sonogashira tandem reaction; 2) Heck/Suzuki 3) Heck/Heck 4) Heck/Hiyama 5) Heck/Cacchi 6) Heck/C−H bond functionalization reaction.

Язык: Английский

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Enantioselective Synthesis of Fused Polycyclic Tropanes via Dearomative [3 + 2] Cycloaddition Reactions of 2-Nitrobenzofurans

Organic Letters, Год журнала: 2019, Номер 22(1), С. 164 - 167

Опубликована: Дек. 23, 2019

A straight synthetic approach to fused polycyclic tropane scaffold formation through an asymmetric dearomatization cycloaddition process of 2-nitrobenzofurans with cyclic azomethine ylides was successfully developed. In the presence a chiral copper complex, derived from Cu(OAc)2 and diphosphine ligand, series derivatives were obtained in high yields (75–91%) excellent enantioselectivities (90–98%). The utility this method showcased by facile transformation product.

Язык: Английский

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Enantioselective dearomative [3+2] cycloaddition of 2-nitrobenzofurans with aldehyde-derived Morita–Baylis–Hillman carbonates

Chemical Communications, Год журнала: 2019, Номер 55(62), С. 9144 - 9147

Опубликована: Янв. 1, 2019

The phosphine-catalyzed asymmetric dearomative [3+2] cycloaddition of 2-nitrobenzofurans with aldehyde-derived Morita-Baylis-Hillman (MBH) carbonates or allenoate was developed. reaction MBH resulted in a series cyclopentabenzofurans containing three contiguous stereocenters good to high yields, diastereoselectivities and enantioselectivities. use also gave the target product moderate enantioselectivity.

Язык: Английский

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Enantioselective Dicarbofunctionalization of Unactivated Alkenes by Palladium‐Catalyzed Tandem Heck/Suzuki Coupling Reaction

Angewandte Chemie, Год журнала: 2019, Номер 131(41), С. 14795 - 14801

Опубликована: Авг. 17, 2019

Abstract A highly enantioselective dicarbofunctionalization of unactivated alkenes was implemented by a Pd‐catalyzed asymmetric tandem Heck/Suzuki coupling reaction. This reaction represents the first example intramolecular cyclization/cross‐coupling olefin‐tethered aryl halides with alkyl‐, alkenyl‐ or arylboronic acids, and provides rapid access to number chiral compounds, such as dihydrobenzofurans, indolines, chromanes, indanes bearing quaternary stereocenter, in good yields excellent enantioselectivities. The practicality this validated modification biologically complex molecules peptides, piperitol, CB2 receptor agonists, etc. Moreover, synthesis two enantiomers can be easily realized simple change order steps sequence.

Язык: Английский

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