Jocic reaction

In organic chemistry, the Jocic reaction, also called the Jocic–Reeve reaction (named after Zivojin Jocic[1] and Wilkins Reeve)[2] is a name reaction that generates α-substituted carboxylic acids from trichloromethylcarbinols and corresponding nucleophiles in the presence of sodium hydroxide. The reaction involves nucleophilic displacement of the hydroxyl group in a 1,1,1-trichloro-2-hydroxyalkyl structure with concomitant conversion of the trichloromethyl portion to a carboxylic acid or similar functional group.

Jocic reaction
Named after Zivojin Jocic
Wilkins Reeve
Reaction type Substitution reaction
Identifiers
Organic Chemistry Portal jocic-reaction

Mechanism

The reaction mechanism involves an epoxide intermediate that undergoes an SN2 reaction by the nucleophile. As a result of this mechanistic aspect, the reaction can easily occur on secondary or tertiary positions, and chiral products can be made by using chiral alcohol substrates.[3][4] The reaction is one stage of the Corey–Link reaction, the Bargellini reaction, and other processes for synthesizing α-amino acids and related structures. Using hydride as the nucleophile, which also reduces the carbonyl of the product, allows this sequence to be used as a homologation reaction for primary alcohols.[5]


Scope

Examples of this reaction include:
Generation of α-azidocarboxylic acids with the use of sodium azide as the nucleophile in DME with the presence of sodium hydroxide.[6]
Conversion of aldehydes to homoelongated carboxylic acids, by first reacting with trichloromethide to form a trichloromethylcarbinol, then undergoing a Jocic reaction with either sodium borohydride or sodium phenylseleno(triethoxy)borate as the nucleophile in sodium hydroxide.[7] This reaction can be followed by the introduction of an amine, to form the corresponding homoelongated amides.[8]

References
  1. Jocic, Zivojin (1897). Zhurnal Russkago Fiziko-Khimicheskago Obshchestva (Journal of the Russian Physical-Chemical Society). 29: 97. Missing or empty |title= (help)
  2. Reeve, Wilkins; McKee, James R.; Brown, Robert; Lakshmanan, Sitarama; McKee, Gertrude A. (1 March 1980). "Studies on the rearrangement of (trichloromethyl)carbinols to α-chloroacetic acids". Canadian Journal of Chemistry. 58 (5): 485–493. doi:10.1139/v80-078.
  3. Reeve, Wilkins (1971). "Reactions of Aryl Trichloromethyl Carbinols with Nucleophiles". Synthesis. 1971 (3): 131–138. doi:10.1055/s-1971-21677.
  4. Shamshina, Julia L.; Snowden, Timothy S. (2006). "Practical Approach to α- or γ-Heterosubstituted Enoic Acids". Org. Lett. 8 (25): 5881–5884. doi:10.1021/ol0625132. PMID 17134296.
  5. Li, Zhexi; Gupta, Manoj K.; Snowden, Timothy S. (2015). "One‐Carbon Homologation of Primary Alcohols and the Reductive Homologation of Aldehydes Involving a Jocic‐Type Reaction". European Journal of Organic Chemistry. 2015 (32): 7009–7019. doi:10.1002/ejoc.201501089.
  6. Corey, Elias James; Link, John O. (1 February 1992). "A general, catalytic, and enantioselective synthesis of α-amino acids". Journal of the American Chemical Society. 114 (5): 1906–1908. doi:10.1021/ja00031a069.
  7. Cafiero, Lauren R.; Snowden, Timothy S. (8 August 2008). "General and Practical Conversion of Aldehydes to Homologated Carboxylic Acids". Organic Letters. 10 (17): 3853–3856. doi:10.1021/ol8016484.
  8. Gupta, Manoj K.; Li, Zhexi; Snowden, Timothy S. (5 March 2014). "Preparation of One-Carbon Homologated Amides from Aldehydes or Primary Alcohols". Organic Letters. 16 (6): 1602–1605. doi:10.1021/ol500200n.
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