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Chemoselective, osmium-free, dihydroxylation/oxidative cleavage of heteroaryl isoprenes by a contemporary Malaprade reaction

Journal Article · · Organic and Biomolecular Chemistry
DOI:https://doi.org/10.1039/d2ob01643e· OSTI ID:2420693
 [1];  [2];  [2];  [2];  [2]
  1. Tennessee Technological Univ., Cookeville, TN (United States); OSTI
  2. Tennessee Technological Univ., Cookeville, TN (United States)
+ Show Author Affiliations
The methyl ketone is a central synthetic building block for the construction of advanced heteroaryl scaffolds and systems. Reactions, including oxidative cyclization strategies, are often predicated on efficient access to this ubiquitous moiety. In the context of arenes, standard approaches leveraging Markovnikov hydration/oxidation or oxidative cleavage of the C–C π bond often afford satisfactory performance. However, when the substrate contains an electron-deficient heteroaryl core, the traditional Malaprade reaction, and related oxidative-cleavage strategies, frequently result in diminished performance over carbon-based arenes. In this work we present the development and application of an oxidative cleavage reaction of various pyridinyl isoprenes towards accessing the downstream methyl ketone for utilization in advanced cyclizations for the preparation of soft-N-donor complexant scaffolds. Further, this efficient protocol parallels the principles of Green chemistry by exchanging KMnO4 for the toxic OsO4 and offers the end-user an efficient, more environmentally friendly option for accessing heteroaryl methyl ketones in one hour of reaction time using potassium permanganate and sodium paraperiodate as a synergistically potent oxidative cleavage system. The wide substrate scope defined access to simple, as well as advanced heteroaryl methyl ketones. Method development, optimization, substrate scope, preliminary mechanistic observations, and a scale up reaction are delineated herein.
Research Organization:
Tennessee Technological Univ., Cookeville, TN (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0018033
OSTI ID:
2420693
Alternate ID(s):
OSTI ID: 1890237
Journal Information:
Organic and Biomolecular Chemistry, Journal Name: Organic and Biomolecular Chemistry Journal Issue: 40 Vol. 20; ISSN 1477-0520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY