For decades, akuammiline alkaloids have attracted synthetic chemists due to their intriguing molecular architecture. Among the different structural elements embedded in their carboskeleton, the methanoquinolizidine system constitutes the signature structural element of this alkaloid family. Herein, we describe a novel synthetic access to this system which relies on a [2,3]-Stevens rearrangement and results in the formal synthesis of strictamine.
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http://dx.doi.org/10.1039/c6cc06125g | DOI Listing |
Nat Commun
June 2024
Institute of Next Generation Matter Transformation, College of Material Sciences Engineering, Huaqiao University, Xiamen, Fujian, 361021, China.
The [1,2]- and [2,3]-Stevens rearrangements are one of the most fascinating chemical bond reorganization strategies in organic chemistry, and they have been demonstrated in a wide range of applications, representing a fundamental reaction tactic for the synthesis of nitrogen compounds in chemical community. However, their applicabilities are limited by the scarcity of efficient, general, and straightforward methods for generating ammonium ylides. Herein, we report a general difluorocarbene-induced tertiary amine-involved [1,2]- and [2,3]-Stevens rearrangements stemmed from in situ generated difluoromethyl ammonium ylides, which allows for the rearrangements of versatile tertiary amines bearing either allyl, benzyl, or propargyl groups, resulting in the corresponding products in one reaction under the same reaction conditions with a general way.
View Article and Find Full Text PDFHemasphere
November 2023
Department of Pathology, Radboud University Medical Center, Nijmegen, The Netherlands.
Patients with lymphoplasmacytic lymphoma/Waldenström macroglobulinemia (LPL/WM) occasionally develop diffuse large B-cell lymphoma (DLBCL). This mostly results from LPL/WM transformation, although clonally unrelated DLBCL can also arise. LPL/WM is characterized by activating (>95%) and mutations (~30%), but the genetic drivers of transformation remain to be identified.
View Article and Find Full Text PDFChem Asian J
December 2023
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Pune, Dr. Homi Bhabha Road, NCL Colony, Pashan, Pune, Maharashtra, 411008, India.
Herein, for the first time we have explored the umpolung reactivity of the vinylogous carbon center of diazo arylidene succinimide (DAS) through rhodium catalysis to achieve [2,3]-Stevens rearrangement of α-thioether esters. The protocol has successfully demonstrated the distal C-H bond functionalization of the α-thioether esters. Alongside, the carbenoid reactivity of DAS has also been achieved with Doyle-Kirmse reaction of allyl/propargyl phenyl sulfides.
View Article and Find Full Text PDFMacromolecules
December 2022
Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
The highly strained -diethylhexyloxy [2.2]paracyclophane-1,9-diene () can be synthesized by ring contraction of a dithia[3.3]paracyclophane using a benzyne-induced Stevens rearrangement.
View Article and Find Full Text PDFAcc Chem Res
February 2022
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China.
α-Diazocarbonyl compounds serve as nucleophiles, dipoles, carbene precursors, and rare electrophiles, enabling a vast array of organic transformations under the influence of metal catalysts. Among them, rearrangement processes are attractive and provide straightforward and efficient accesses to one-carbon extension adducts or heteroatom-containing molecules. The reactions occur upon the release of dinitrogen after nucleophilic addition or before ylide formation.
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