1 CHE 3332 – Organic Chemistry 2 – Spring 2021 Week 12 Resource

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1 CHE 3332 – Organic Chemistry 2 – Spring 2021 Week 12 Resource

CHE 3332 – Organic Chemistry 2 – Spring 2021 Week 12 Resource Hello everyone! Virtual group tutoring for this class will be every Tuesday from 6-7 pm, and you can reserve your spot by making an appointment at www.Baylor.edu/Tutoring. This week, we’ll cover Chapter 21: Carboxylic Acid Derivatives. Keywords: carboxylic acid, acid halide, ester, amide, nitrile, anhydride Carboxylic Acids These are the reactions that make carboxylic acids (review from previous chapters): 1. Ozonolysis of alkyne 2. Oxidation of primary alcohol 3. Oxidation at benzylic position 4. Hydrolysis of nitrile 5. Carboxylation of Grignard Reactions that start with carboxylic acid: 1. Reduction with LAH or BH3. LAH is very powerful and reduces everything; BH3 is more selective and only reduces the carboxylic acid substituent. 2. Substitution – proton transfers can happen at any step 1 Acid Halides Reaction that makes acid halide with SOCl2 or COCl2 (chair lift reaction!): Reactions that start with acid halide: 1. Make a carboxylic acid 2. Make an ester – acyl substitution 3. Make an amide 4. Reduction to alcohol or aldehyde 5. Make an anhydride 6. React with Grignard or Gilman Acid Anhydrides Reactions that make acid anhydride: 1. From carboxylic acid 2. From acid halide as shown on page 2. 2 Esters Reactions that make esters: 1. From a carboxylic acid – SN2 2. Fischer Esterification 3. From acid halide as shown on page 2. Reactions that start with esters: 1. Transesterification – an ester turns into a new ester 2. Make a carboxylic acid with acid or base catalyzed reagents 3. Make an amide 4. Reduction to aldehyde or alcohol. Reduction to alcohol is done with LAH as previously shown on page 2. For reduction to aldehyde, instead of using LiAlH, DIBAL, is used. 5. React with Grignard as shown on page 2. 3 Amides Reactions to make amides: 1. From anhydride 2. From acid halide as shown on page 2. 3. From ester as shown on page 3. Reactions that start with amides: 1. Make a carboxylic acid with acid or base catalyzed reagents as shown on page 3. 2. Reduction to amine with LAH as shown on page 2. Nitriles Reactions to make nitriles: 1. Alkylate a cyanide 2. From amide Reactions that start with nitriles: 1. React with Grignard to make a ketone 2. Make a carboxylic acid with acid or base catalyzed reagents as shown on page 3. 3. Reduction to amine with LAH as shown on page 2. 4 Quiz: 1. Predict the product: 2. Propose a synthesis: 3. Propose a synthesis: Answers: Notes & questions sourced from Wiley Organic Chemistry Second Semester textbook. 1. 2. 3. 5 .

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Amide Activation: an Emerging Tool for Chemoselective Synthesis
Featuring work from the research group of Professor As featured in: Nuno Maulide, University of Vienna, Vienna, Austria Amide activation: an emerging tool for chemoselective synthesis Let them stand out of the crowd – Amide activation enables the chemoselective modification of a large variety of molecules while leaving many other functional groups untouched, making it attractive for the synthesis of sophisticated targets. This issue features a review on this emerging field and its application in total synthesis. See Nuno Maulide et al., Chem. Soc. Rev., 2018, 47, 7899. rsc.li/chem-soc-rev Registered charity number: 207890 Chem Soc Rev View Article Online REVIEW ARTICLE View Journal | View Issue Amide activation: an emerging tool for chemoselective synthesis Cite this: Chem. Soc. Rev., 2018, 47,7899 Daniel Kaiser, Adriano Bauer, Miran Lemmerer and Nuno Maulide * It is textbook knowledge that carboxamides benefit from increased stabilisation of the electrophilic carbonyl carbon when compared to other carbonyl and carboxyl derivatives. This results in a considerably reduced reactivity towards nucleophiles. Accordingly, a perception has been developed of amides as significantly less useful functional handles than their ester and acid chloride counterparts. Received 27th April 2018 However, a significant body of research on the selective activation of amides to achieve powerful DOI: 10.1039/c8cs00335a transformations under mild conditions has emerged over the past decades. This review article aims at placing electrophilic amide activation in both a historical context and in that of natural product rsc.li/chem-soc-rev synthesis, highlighting the synthetic applications and the potential of this approach. Creative Commons Attribution 3.0 Unported Licence.
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