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DOI: 10.1055/a-2004-1093
Efficient Synthesis and Functionalization of 3-Bromonaphtho[2,3-b]thiophene
This work was supported by the Natural Sciences and Engineering Research Council of Canada (NSERC) through a Discovery Grant (2017-04297), an Idea to Innovation Grant (I2IPJ 523283-18), and the CREATE Training Program in BioActives (510963). Newfoundland and Labrador (Labrador’s Post-Secondary Student Support Program) and the Nova Scotia Graduate Scholarship are thanked for graduate funding to E.N.W.
Abstract
Naphtho[2,3-b]thiophene is a linear sulfur-containing polycyclic aromatic hydrocarbon. Naphtho[2,3-b]thiophene and its derivatives are commonly accessed by a Bradsher cyclization. Synthesis of the Bradsher cyclization substrate typically requires harsh conditions, including several oxidation state changes. Here, we report an improved, multigram synthesis of 3-bromonaphtho[2,3-b]thiophene, exploiting a copper-catalyzed cross-coupling to prepare the Bradsher substrate in three steps from commercial materials while minimizing redox reactions. In this work, the 3-bromonaphthothiophene is further functionalized via lithium–halogen exchange, with the key finding being a specific order of addition in lithiation is required to avoid undesired rearrangement reactions. Transformation to a versatile set of derivatives, including a naphthothiophene-containing chiral amine, is illustrated.
Keywords
naphtho[2,3-b]thiophenes - Bradsher cyclization - copper catalysis - cross-coupling - lithiationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2004-1093.
- Supporting Information
Publication History
Received: 16 November 2022
Accepted after revision: 26 December 2022
Accepted Manuscript online:
26 December 2022
Article published online:
25 January 2023
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