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Literature DB >> 28981290

Mechanistic Duality in Tertiary Amine Additions to Thermally Generated Hexadehydro-Diels-Alder Benzynes.

Sean P Ross¹, Beeraiah Baire¹, Thomas R Hoye¹.

Abstract

Reported here are studies directed at understanding the mechanism of tertiary amine addition to hexadehydro-Diels-Alder (HDDA)-generated benzynes. Tertiary amines are presumed to engage benzynes by generation of a zwitterionic intermediate. Simple trialkylamines undergo intermolecular protonation by a protic nucleophile to give an aryl ammonium intermediate that is then dealkylated. Amines containing acidified β-protons undergo an intramolecular elimination to give the aniline and an alkene. Finally, amino alcohols react at either of their N- or O atoms, depending upon the extent of internal hydrogen bonding.

Entities: Chemical Species

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Year: 2017 PMID： 28981290 PMCID： PMC5650509 DOI： 10.1021/acs.orglett.7b02888

Source DB: PubMed Journal: Org Lett ISSN： 1523-7052 Impact factor: 6.005

27 in total

Review 1. A comprehensive history of arynes in natural product total synthesis.

Authors: Pamela M Tadross; Brian M Stoltz
Journal: Chem Rev Date: 2012-03-23 Impact factor: 60.622

2. N-Arylation of Tertiary Amines under Mild Conditions.

Authors: Maayan Hirsch; Shubhendu Dhara; Charles E Diesendruck
Journal: Org Lett Date: 2016-02-23 Impact factor: 6.005

3. Employing arynes in transition-metal-free monoarylation of aromatic tertiary amines.

Authors: Sachin Suresh Bhojgude; Trinadh Kaicharla; Akkattu T Biju
Journal: Org Lett Date: 2013-10-14 Impact factor: 6.005

4. Synthesis of functionalized amino epoxides by a three-component coupling involving aziridines, arynes and aldehydes.

Authors: Tony Roy; Manikandan Thangaraj; Rajesh G Gonnade; Akkattu T Biju
Journal: Chem Commun (Camb) Date: 2016-07-12 Impact factor: 6.222

5. Regioselectivity in the nucleophile trapping of arynes: the electronic and steric effects of nucleophiles and substituents.

Authors: Rajdip Karmakar; Sang Young Yun; Kung-Pern Wang; Daesung Lee
Journal: Org Lett Date: 2013-12-06 Impact factor: 6.005

6. Indolyne and aryne distortions and nucleophilic regioselectivites.

Authors: Paul H-Y Cheong; Robert S Paton; Sarah M Bronner; G-Yoon J Im; Neil K Garg; K N Houk
Journal: J Am Chem Soc Date: 2010-02-03 Impact factor: 15.419

7. Strain-induced regioselectivities in reactions of benzyne possessing a fused four-membered ring.

Authors: Toshiyuki Hamura; Yousuke Ibusuki; Kazuhiko Sato; Takashi Matsumoto; Yoshihiro Osamura; Keisuke Suzuki
Journal: Org Lett Date: 2003-10-02 Impact factor: 6.005

8. Three-component reaction of small-ring cyclic amines with arynes and acetonitrile.

Authors: David Stephens; Yu Zhang; Mathew Cormier; Gabriel Chavez; Hadi Arman; Oleg V Larionov
Journal: Chem Commun (Camb) Date: 2013-06-14 Impact factor: 6.222

9. Synthesis of N-Aryl β-Amino Alcohols by Trifluoroacetic Acid Promoted Multicomponent Coupling of Aziridines, Arynes, and Water.

Authors: Tony Roy; Dnyaneshwar R Baviskar; Akkattu T Biju
Journal: J Org Chem Date: 2015-10-15 Impact factor: 4.354

Mechanistic Duality in Tertiary Amine Additions to Thermally Generated Hexadehydro-Diels-Alder Benzynes.

Review 1. A comprehensive history of arynes in natural product total synthesis.

2. N-Arylation of Tertiary Amines under Mild Conditions.

3. Employing arynes in transition-metal-free monoarylation of aromatic tertiary amines.

4. Synthesis of functionalized amino epoxides by a three-component coupling involving aziridines, arynes and aldehydes.

5. Regioselectivity in the nucleophile trapping of arynes: the electronic and steric effects of nucleophiles and substituents.

6. Indolyne and aryne distortions and nucleophilic regioselectivites.

7. Strain-induced regioselectivities in reactions of benzyne possessing a fused four-membered ring.

8. Three-component reaction of small-ring cyclic amines with arynes and acetonitrile.

9. Synthesis of N-Aryl β-Amino Alcohols by Trifluoroacetic Acid Promoted Multicomponent Coupling of Aziridines, Arynes, and Water.

10. The distorted tropane of scopoline.

1. Reactions of Diaziridines with Benzynes Give N-Arylhydrazones.

2. Reactions of HDDA Benzynes with C,N-Diarylimines (ArCH=NAr').

Review 3. Hexadehydro-Diels-Alder Reaction: Benzyne Generation via Cycloisomerization of Tethered Triynes.

4. Reactions of thermally generated benzynes with six-membered N-heteroaromatics: pathway and product diversity.