Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(8), P. 4373 - 4505

Published: March 19, 2021

This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution decarboxylative oxidative substitutions. For each reaction, catalytic data, as well examples of their application to synthesis complex molecules, are collected. Sections which we discuss key aspects for high selectivity a comparison with other metals (with advantages disadvantages) also included. asymmetric substitution, data grouped according type nucleophile employed. Because prominent position use stabilized carbon nucleophiles heteronucleophiles, many chiral ligands have been developed. To better compare results, they presented by ligand types. reactions mainly promoted PHOX or Trost ligands, justifies organizing this section chronological order. results used.

Language: Английский

---

Covalent organic frameworks

Nature Reviews Methods Primers, Journal Year: 2023, Volume and Issue: 3(1)

Published: Jan. 12, 2023

Language: Английский

---

Asymmetric Ni-Catalyzed Radical Relayed Reductive Coupling

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(31), P. 13515 - 13522

Published: June 29, 2020

Alkene dicarbofunctionalizations enable the streamlined construction of aliphatic structures and have thus been subject intense research efforts. Despite significant progress, catalytic asymmetric variants remain scarce. Inspired by advantages reductive cross-coupling approaches, we present here a highly efficient intermolecular Ni-catalyzed dicarbofunctionalization alkenes. Two distinct readily available electrophiles, namely, Csp2- Csp3-halides, are added simultaneously across variety olefins (vinyl amides, vinyl boranes, phosphonates) at room temperature in regio- enantioselective manner. The reaction, devoid sensitive organometallic reagents, takes advantage an situ generated chiral alkyl Ni(III)-intermediate to ensure stereodefined outcome Csp3–Csp2 bond-forming reaction. An (l)-(+)-isoleucine bisoxazoline ligand presence coordinating sites on alkene key for successful these "asymmetric radical relayed couplings" (ARRRCs). Further, multiple transformations amides obtained this process showcase potential new methodology straightforward assembly building blocks such as primary secondary amines oxazolines, highlighting its synthetic utility.

Language: Английский

---

gem-Diborylalkanes: recent advances in their preparation, transformation and application

Organic & Biomolecular Chemistry, Journal Year: 2018, Volume and Issue: 16(7), P. 1050 - 1064

Published: Jan. 1, 2018

Recently,gem-diborylalkanes have attracted much attention as versatile building blocks and fundamental intermediates in organic synthesis, because they enable multiple C–C bond construction further transformation at C–B bonds.

Language: Английский

---

Merging Ketyl Radical Chemistry and Allylboration via Strain Release: One-Pot Multicomponent Access to Sterically Congested Ketone-Functionalized Organoborons

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 17, 2025

Ketyl radical-mediated ring opening and [2σ+2π] cycloaddition of cyclopropyl ketones (CPKs) with alkynes typically require activation by alkyl, aryl, or carbonyl groups yielding cyclopentenes having one two non-adjacent stereocenters. We developed a one-pot multicomponent reaction diboryl-activated CPKs aldehydes that merges ketyl radical chemistry allylboration. This method enabled highly diastereoselective access to densely functionalized featuring homoallylic alcohol, ketone, alkenyl boronate motifs on adjacent quaternary, tertiary, secondary stereogenic centers. Additionally, diboryl also allowed the synthesis rare ketone-functionalized γ,γ-disubstituted allylic diborons.

Language: Английский

---

A Copper(I)‐Catalyzed Enantioselective γ‐Boryl Substitution of Trifluoromethyl‐Substituted Alkenes: Synthesis of Enantioenriched γ,γ‐gem‐Difluoroallylboronates

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(24), P. 7196 - 7199

Published: April 27, 2018

Abstract The first catalytic enantioselective γ‐boryl substitution of CF 3 ‐substituted alkenes is reported. A series was treated with a diboron reagent in the presence copper(I)/Josiphos catalyst to afford corresponding optically active γ,γ‐ gem ‐difluoroallylboronates high enantioselectivity. thus obtained products could be readily converted into difluoromethylene‐containing homoallylic alcohols using highly stereospecific allylation reactions.

Language: Английский

---

Heck Reaction of Electronically Diverse Tertiary Alkyl Halides

Organic Letters, Journal Year: 2018, Volume and Issue: 20(2), P. 357 - 360

Published: Jan. 5, 2018

The efficient Pd-catalyzed Heck reaction of diverse tertiary alkyl halides with alkenes has been developed. Unactivated efficiently react at room temperature under visible light irradiation no exogenous photosensitizers required. For activated halides, the same catalytic system works well without light. These methods offer a general access to electronically possessing quaternary and functionalized allylic carbon centers. substituents these centers include alkyl-, carbalkoxy-, tosyl-, phosphonyl-, boronate groups. It was also shown that end-game mechanism this transformation may vary depending on type substrates used.

Language: Английский

---

Electrochemically Enabled Carbohydroxylation of Alkenes with H₂O and Organotrifluoroborates

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(48), P. 16387 - 16391

Published: Nov. 2, 2018

Unprecedented hydroxy-alkynylation and -alkenylation reactions of arylalkenes have been developed through electrochemically enabled addition an organotrifluoroborate reagent H2O across the double bond alkene. The use electrochemistry to promote these oxidative alkene 1,2-difunctionalization not only obviates need for transition-metal catalysts oxidizing reagents but also ensures high regio- chemoselectivity afford homopropargylic or homoallylic alcohols. possibility extending electrochemical difunctionalization strategy other carbo-heterofunctionalization has demonstrated.

Language: Английский

---

Soft 2D nanoarchitectonics

NPG Asia Materials, Journal Year: 2018, Volume and Issue: 10(4), P. 90 - 106

Published: April 1, 2018

Nanoarchitectonics is a new paradigm to combine and unify nanotechnology with other sciences technologies, such as supramolecular chemistry, self-assembly, self-organization, materials technology for manipulation of the size material objects, even biotechnology hybridization bio-components. The nanoarchitectonic concept leads synergistic combination various methodologies in production, including atomic/molecular-level control, field-controlled organization. focus this review on soft 2D nanoarchitectonics. Scientific views nanomaterials are not fully established compared those rigid materials. Here, we collect recent examples constructions functional systems components. These selected according following three categories basis spatial density motional freedom: (i) well-packed oriented organic rational design component molecules device applications, (ii) well-defined assemblies porous structures network materials, (iii) control molecular machines receptors certain freedom confined two dimensions. pursuit ever smaller has required be combined fields or biomolecules—these approaches now unified ‘nanoarchitectonics’. A Japan-based team led by Katsuhiko Ariga at National Institute Materials Science Tsukuba developments traditionally less explored than graphene. Sheets composed held together weak forces, typically hydrogen bonding metal coordination, have been constructed that serve crystalline semiconductors, machines, receptors. film living cells also obtained liquid–liquid interface. achievements show nanoarchitectonics holds great promise variety ranging from electronics biomaterials. target because scientific presented freedoms: controls nature plain.

Language: Английский

---

Electroreductive Olefin–Ketone Coupling

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(50), P. 20979 - 20986

Published: Dec. 1, 2020

A user-friendly approach is presented to sidestep the venerable Grignard addition unactivated ketones access tertiary alcohols by reversing polarity of disconnection. In this work a ketone instead acts as nucleophile when adding simple olefins accomplish same overall transformation. The scope coupling broad enabled using an electrochemical approach, and reaction scalable, chemoselective, requires no precaution exclude air or water. Multiple applications demonstrate simplifying nature on multistep synthesis, mechanistic studies point intuitive mechanism reminiscent other chemical reductants such SmI2 (which cannot reaction).

Language: Английский

---