Related Experiment Video

Updated: May 27, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
06:46

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Published on: June 21, 2017

Enantioselective decarboxylative alkylation reactions: catalyst development, substrate scope, and mechanistic studies

Douglas C Behenna1, Justin T Mohr, Nathaniel H Sherden

  • 1The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., MC 101-20, Pasadena, CA 91125, USA.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|November 16, 2011
PubMed
Summary

This study introduces a new method for creating α-quaternary ketones using enantioselective alkylations. Palladium complexes with phosphinooxazoline (PHOX) ligands enable high yields and enantioselectivity with various enolate precursors.

More Related Videos

Enzymatic Cascade Reactions for the Synthesis of Chiral Amino Alcohols from L-lysine09:14

Enzymatic Cascade Reactions for the Synthesis of Chiral Amino Alcohols from L-lysine

Published on: February 16, 2018

Achieving Moderate Pressures in Sealed Vessels Using Dry Ice As a Solid CO2 Source06:26

Achieving Moderate Pressures in Sealed Vessels Using Dry Ice As a Solid CO2 Source

Published on: August 17, 2018

Related Concept Videos

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
Preparation of Alkynes: Alkylation Reaction02:27

Preparation of Alkynes: Alkylation Reaction

Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Factors Affecting α-Alkylation of Ketones: Choice of Base01:10

Factors Affecting α-Alkylation of Ketones: Choice of Base

α-Alkylation of ketones is achieved in the presence of alkyl halides and a base. The reaction proceeds via the formation of an enolate ion followed by nucleophilic substitution. The choice of base employed is essential as it is the key factor in determining the reaction outcome.
The reaction involving bases like EtO− whose conjugate acid EtOH (pKa = 15.9) is stronger than the ketone (pKa = 19.2) results in an equilibrium mixture with higher ketone concentration. As a consequence, side reactions...
α-Alkylation of Ketones via Enolate Ions01:10

α-Alkylation of Ketones via Enolate Ions

Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the strong interaction...
Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation01:22

Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation

Baeyer–Villiger oxidation converts aldehydes to carboxylic acids and ketones to esters. The reaction uses peroxy acids or peracids and is often catalyzed by acid. The reaction is named after its pioneers, Adolf von Baeyer and Victor Villiger. The reaction is achieved by a wide range of peracids such as m-chloroperoxybenzoic acid (mCPBA), perbenzoic acid (C6H5COOOH), peracetic acid (CH3COOOH), hydrogen peroxide (H2O2), and tert-butyl hydroperoxide (t-BuOOH).
The carbonyl center is activated by...