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通过1,4-迈克尔在Penicillium crustosum中形成烯和烯酸 添加来自Hydroxyclavatol的ortho-Quinone Methide到来自Crustosic Acid的γ-Butyrolactones

  • 0Institut für Pharmazeutische Biologie und Biotechnologie, Philipps-Universität Marburg , Robert-Koch-Strasse 4 , Marburg 35037 , Germany.

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Conjugate Addition of Enolates: Michael Addition 01:08

3.6K

The attack of a nucleophile at the β carbon of an α,β-unsaturated carbonyl compound is called conjugate addition. Conjugate addition reactions of active methylene compounds, such as β-diketones, β-keto esters, β-keto nitriles, and α-nitro ketones, are called Michael addition reactions.

The reaction is catalyzed by a base that abstracts the acidic methylene hydrogen, generating a doubly-stabilized enolate ion that serves as the nucleophile or the Michael donor. The base employed depends...

Conjugate Addition (1,4-Addition) vs Direct Addition (1,2-Addition) 01:27

4.3K

α,β-Unsaturated carbonyl compounds with two electrophilic sites, the carbonyl carbon, and the β carbon, are susceptible to nucleophilic attack via two modes: conjugate or 1,4-addition and direct or 1,2-addition.
Conjugate addition results in a thermodynamically stable product. The reaction retains the stronger C=O bond at the expense of the weaker C=C π bond. The process is slow as the β carbon is less electrophilic than the carbonyl carbon.
Direct addition products are...

Radical Formation: Addition 00:47

2.3K

Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...

Electrophilic 1,2- and 1,4-Addition of X<sub data-lazy-src=

3.5K

Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.

Conjugated dienes react with halogens in a similar manner. However, in addition to the 1,2-dihalide, they also form a 1,4-dihalide. The mechanism involves two steps.
First, a nucleophilic attack by one of the diene π bonds on the electrophilic center of the polarized halogen molecule forms a halonium ion intermediate. This is followed by a nucleophilic attack of the...

Electrophilic 1,2- and 1,4-Addition of HX to 1,3-Butadiene 01:17

8.0K

The electrophilic addition of hydrogen halides such as HBr to alkenes and nonconjugated dienes gives a single product as per Markovnikov’s rule.

With conjugated systems like 1,3-butadiene, the addition of one equivalent of HBr yields a mixture of products: 1,2 and 1,4-addition products. As shown below, the mechanism involves the addition of H+ across one of the double bonds of the conjugated diene to form a resonance stabilized allyl cation. This is followed by the nucleophilic attack of...

Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation 01:27

2.9K

Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).

The ring-forming reaction occurs in two stages: Michael addition and the subsequent intramolecular aldol condensation....