As has been well-recognized, semipinacol rearrangement functions as an exceptionally useful methodology in the synthesis of β-functionalized ketones, creation of quaternary carbon centers, and construction of challenging carbocycles. Due to their versatile utilities in organic synthesis, development of novel rearrangement reactions has been a vibrant topic that continues to shape the research field. Recent breakthroughs in novel electrophiles, tandem processes, and enantioselective catalytic transformations further enrich the toolbox of this chemistry and spur the strategic applications of this methodology in natural product synthesis. These achievements will be discussed in this minireview.
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http://dx.doi.org/10.1039/d1sc02386a | DOI Listing |
J Org Chem
October 2024
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China.
On the basis of the chiral ion pair between catalytic anionic stereogenic-at-cobalt(III) complexes and halonium ion intermediates, an asymmetric halogenation/semipinacol rearrangement reaction has been established using -bromosuccinimide as the halogen source. This protocol provides an alternative approach for accessing a diverse set of chiral β-bromocycloketones in good yields with high enantioselectivities (≤96% yield, 95.5:4.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
EaStCHEM, School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK.
A highly enantioselective cobalt-catalyzed semipinacol rearrangement of symmetric α,α-diarylallylic alcohols is disclosed. A chiral cobalt-salen catalyst generates a highly electrophilic carbocation surrogate following hydrogen atom transfer and radical-polar crossover steps. This methodology provides access to enantioenriched α-aryl ketones through invertive displacement of a cobalt(IV) complex during 1,2-aryl migration.
View Article and Find Full Text PDFChem Commun (Camb)
October 2024
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, P. R. China.
J Am Chem Soc
September 2024
New Cornerstone Science Laboratory, State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
The highly efficient synthesis of chiral indolines fused with an azabicyclo[2.2.1]heptanone moiety is achieved by an asymmetric dearomatization reaction of indoles with cyclobutanones.
View Article and Find Full Text PDFOrg Lett
September 2024
School of Chemistry, Key Laboratory of Advanced Technologies of Material, Ministry of Education, Southwest Jiaotong University, Chengdu 610031, P. R. China.
A bioinspired total synthesis of 3--junipercedrol, which contains a strained tricyclo[5.2.2.
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