Chemistry of Tertiary Carbon Center in the Formation of Congested C−O Ether Bonds

Nucleophilic substitutions, including SN1 and SN2, are classical and reliable reactions, but a serious drawback is their intolerance for both bulky nucleophiles and chiral tertiary alkyl electrophiles for the synthesis of a chiral quaternary carbon center. An SRN1 reaction via a radical species is a...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2021-02, Vol.60 (8), p.4329-4334
Main Authors: Hirata, Goki, Takeuchi, Kentarou, Shimoharai, Yusuke, Sumimoto, Michinori, Kaizawa, Hazuki, Nokami, Toshiki, Koike, Takashi, Abe, Manabu, Shirakawa, Eiji, Nishikata, Takashi
Format: Article
Language:English
Subjects:
Alcohols
alkylation
amide
Carbon
etherification
Halides
Intolerance
Nucleophiles
substitution
Substitution reactions
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Summary:Nucleophilic substitutions, including SN1 and SN2, are classical and reliable reactions, but a serious drawback is their intolerance for both bulky nucleophiles and chiral tertiary alkyl electrophiles for the synthesis of a chiral quaternary carbon center. An SRN1 reaction via a radical species is another conventional method used to carry out substitution reactions of bulky nucleophiles and alkyl halides, but chiral tertiary alkyl electrophiles cannot be used. Therefore, a stereospecific nucleophilic substitution reaction using chiral tertiary alkyl electrophiles and bulky nucleophiles has not yet been well studied. In this paper, we describe the reaction of tertiary alkyl alcohols and non‐chiral or chiral α‐bromocarboxamides as a tertiary alkyl source for the formation of congested ether compounds possessing two different tertiary alkyl groups on the oxygen atom with stereoretention. Cs2CO3 reaction system enables stereospecific reaction of functionalized tertiary alkyl bromides and bulky alcohols. The reaction occurred with retention of configuration.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202010697