Tandem Synthesis of 9,10-Dihydro-9,10-diboraanthracenes via Elusive ortho-Lithiated Phenylboronates

Sergiusz Luliński , Jaromir Smętek , Krzysztof Durka , Janusz Serwatowski

Abstract

A simple general protocol is reported for the synthesis of functionalised 9,10-dihydroxy-9,10-dihydro-9,10-diboraanthracenes by treatment of the appropriate substituted (2-halophenyl)boronates with tBuLi. The reaction apparently occurs through the formation of ortho-lithiated phenylboronates. These elusive species possess a trivalent Lewis-acidic boron atom in the vicinity of a strongly nucleophilic lithiated carbon atom. The results of DFT calculations indicate that Br/Li exchange is kinetically favored over nucleophilic alkylation of the boron atom, which contrasts with the behaviour of the sterically less hindered nBuLi. The results are consistent with lower yields of 9,10-dihydro-9,10-diboraanthracenes obtained by using the latter reagent. Subsequent steps of the cascade reaction sequence involve trapping of the reactive lithium/boron intermediate in situ with the starting boronate, followed by a second halogen/lithium exchange and final ring closure. Isolation of 9,10-dihydroxy-9,10-dihydro-9,10-diboraanthracenes was further aided by their complexation with 8-hydroxyquinoline.
Author Sergiusz Luliński (FC / DPC)
Sergiusz Luliński,,
- Department Of Physical Chemistry
, Jaromir Smętek (FC / DPC)
Jaromir Smętek,,
- Department Of Physical Chemistry
, Krzysztof Durka (FC / DPC)
Krzysztof Durka,,
- Department Of Physical Chemistry
, Janusz Serwatowski (FC / DPC)
Janusz Serwatowski,,
- Department Of Physical Chemistry
Journal seriesEuropean Journal of Organic Chemistry, ISSN 1434-193X, [1099-0690]
Issue year2013
Vol2013
No36
Pages8315-8322
Publication size in sheets0.5
Keywords in EnglishHeterocycles, Lithiation, Halogens, Borates, Density functional calculations
ASJC Classification1605 Organic Chemistry; 1606 Physical and Theoretical Chemistry
DOIDOI:10.1002/ejoc.201300868
URL http://onlinelibrary.wiley.com/doi/10.1002/ejoc.201300868/abstract
ProjectBimetallic compounds derived from heteroarylboranes – new attractive building blocks for organic synthesis and material chemistry. Project leader: Luliński Sergiusz, , start date 29-08-2012, planned end date 28-08-2015, 505G/1020/0066000, Implemented
WCh Projects financed by NSC [Projekty finansowane przez NCN]
Languageen angielski
File
Luli-ski_et_al-2013-European_Journal_of_Organic_Chemistry.pdf 538.39 KB
Score (nominal)35
Score sourcejournalList
ScoreMinisterial score = 35.0, 07-09-2020, ArticleFromJournal
Ministerial score (2013-2016) = 35.0, 07-09-2020, ArticleFromJournal
Publication indicators Scopus Citations = 17; WoS Citations = 16; GS Citations = 1.0; Scopus SNIP (Source Normalised Impact per Paper): 2013 = 0.834; WoS Impact Factor: 2013 = 3.154 (2) - 2013=3.001 (5)
Citation count*1 (2014-12-11)
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* presented citation count is obtained through Internet information analysis and it is close to the number calculated by the Publish or Perish system.
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