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12.14 : Acetals and Thioacetals as Protecting Groups for Aldehydes and Ketones

Acetals are formed by reacting two equivalents of alcohol with carbonyl compounds like aldehydes or ketones. Acetals are unaffected by bases, nucleophiles, oxidizing agents, and reducing agents. They serve as protecting groups for aldehydes and ketones. Acetals can be easily formed and also easily removed via mild acid hydrolysis.

In the presence of multiple functional groups, when selective reduction of one group over the other is desired, groups like aldehydes and ketones that form acetals readily can be protected from undergoing undesirable reactions. For instance, if a compound contains a ketone and an ester group, the ketone can be protected by converting it into acetal. On the other hand, the ester does not form acetal; hence it can be subjected to the desired reaction, and inthe end, the ketone can be deprotected.

Figure1

The sulfur-containing analogs of acetals are called thioacetals thatcan act as an efficient protecting group for aldehydes and ketones. The thioacetals are stable in acidic conditions. Due to this, they cannot be deprotected by acid hydrolysis. Instead, mercuric chloride in aqueous acetonitrile is used for its deprotection.

Figure2

Apart from acting as protecting groups, thioacetals also play a major role in organic synthesis, especially in reduction reactions. Thioacetals can undergo desulfurization in the presence of Raney nickel and hydrogen to form hydrocarbons.

Figure3

Tags
AcetalsThioacetalsProtecting GroupsAldehydesKetonesAcid HydrolysisSelective ReductionDesulfurizationRaney Nickel

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12.14 : Acetals and Thioacetals as Protecting Groups for Aldehydes and Ketones

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12.1 : Structures of Aldehydes and Ketones

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12.2 : IUPAC Nomenclature of Aldehydes

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12.3 : IUPAC Nomenclature of Ketones

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12.7 : Preparation of Aldehydes and Ketones from Alcohols, Alkenes, and Alkynes

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12.8 : Preparation of Aldehydes and Ketones from Nitriles and Carboxylic Acids

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12.9 : Preparation of Aldehydes and Ketones from Carboxylic Acid Derivatives

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12.10 : Nucleophilic Addition to the Carbonyl Group: General Mechanism

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12.11 : Aldehydes and Ketones with Water: Hydrate Formation

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12.12 : Aldehydes and Ketones with Alcohols: Hemiacetal Formation

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12.13 : Protecting Groups for Aldehydes and Ketones: Introduction

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