Literature DB >> 15535677

Formation of benzynes from 2,6-dihaloaryllithiums: mechanistic basis of the regioselectivity.

Antonio Ramírez1, John Candler, Crystal G Bashore, Michael C Wirtz, Jotham W Coe, David B Collum.   

Abstract

The key elimination step for the formation of 3-chloro- and 3-fluorobenzyne from 2-chloro-6-fluorophenyllithium displays a pronounced solvent-dependent regioselectivity. 6Li and 13C NMR spectroscopic studies on 2-chloro-6-fluorophenyllithium reveal a single monomeric aryllithium, suggested by DFT computational studies to be a trisolvate. Rate studies indicate that the elimination of LiCl and LiF proceeds via trisolvated and disolvated monomers, respectively.

Entities:  

Mesh:

Substances:

Year:  2004        PMID: 15535677     DOI: 10.1021/ja044899m

Source DB:  PubMed          Journal:  J Am Chem Soc        ISSN: 0002-7863            Impact factor:   15.419


  8 in total

1.  Mechanism of lithium diisopropylamide-mediated substitution of 2,6-difluoropyridine.

Authors:  Mihai S Viciu; Lekha Gupta; David B Collum
Journal:  J Am Chem Soc       Date:  2010-05-12       Impact factor: 15.419

2.  Azaaldol condensation of a lithium enolate solvated by N,N,N',N'-tetramethylethylenediamine: dimer-based 1,2-addition to imines.

Authors:  Timothy S De Vries; Angela M Bruneau; Lara R Liou; Hariharaputhiran Subramanian; David B Collum
Journal:  J Am Chem Soc       Date:  2013-03-04       Impact factor: 15.419

3.  Regioselective lithium diisopropylamide-mediated ortholithiation of 1-chloro-3-(trifluoromethyl)benzene: role of autocatalysis, lithium chloride catalysis, and reversibility.

Authors:  Alexander C Hoepker; Lekha Gupta; Yun Ma; Marc F Faggin; David B Collum
Journal:  J Am Chem Soc       Date:  2011-04-18       Impact factor: 15.419

4.  Transition-metal-free alkynylation of aryl chlorides.

Authors:  Thanh Truong; Olafs Daugulis
Journal:  Org Lett       Date:  2011-07-25       Impact factor: 6.005

5.  Aryl Carbamates: Mechanisms of Orthosodiations and Snieckus-Fries Rearrangements.

Authors:  Yun Ma; Ryan A Woltornist; Russell F Algera; David B Collum
Journal:  J Org Chem       Date:  2019-07-01       Impact factor: 4.354

6.  Autocatalysis in lithium diisopropylamide-mediated ortholithiations.

Authors:  Kanwal J Singh; Alexander C Hoepker; David B Collum
Journal:  J Am Chem Soc       Date:  2008-12-31       Impact factor: 15.419

7.  Anionic Snieckus-Fries rearrangement: solvent effects and role of mixed aggregates.

Authors:  Jason C Riggs; Kanwal J Singh; Ma Yun; David B Collum
Journal:  J Am Chem Soc       Date:  2008-09-18       Impact factor: 15.419

8.  Lithium diisopropylamide-mediated lithiation of 1,4-difluorobenzene under nonequilibrium conditions: role of monomer-, dimer-, and tetramer-based intermediates and lessons about rate limitation.

Authors:  Jun Liang; Alexander C Hoepker; Angela M Bruneau; Yun Ma; Lekha Gupta; David B Collum
Journal:  J Org Chem       Date:  2014-08-08       Impact factor: 4.354

  8 in total

北京卡尤迪生物科技股份有限公司 © 2022-2023.