ChemInform Abstract: RING EXPANSION OF 2-ETHYNYLTHIACYCLOALKANES VIA SULFONIUM YLIDES BY (2,3)-SIGMATROPIC REARRANGEMENT

1983 ◽  
Vol 14 (15) ◽  
Author(s):  
H. SASHIDA ◽  
M. TSUCHIYA
Keyword(s):  
Ring Expansion ◽  
Sigmatropic Rearrangement ◽  
Sulfonium Ylides

scholarly journals Intermolecular 3+3 Ring Expansion of Aziridines to Dehydropiperidines through the Intermediacy of Aziridinium Ylides

2019 ◽  
Author(s):  
Jennifer Schomaker ◽  
Josephine Eshon ◽  
Kate A. Nicastri ◽  
Steven C. Schmid ◽  
William T. Raskopf ◽  
...  
Keyword(s):  
Natural Product ◽  
Functional Group ◽  
Ring Expansion ◽  
Sigmatropic Rearrangement ◽  
Reactive Intermediate ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Complex Molecules ◽  
Form Complex ◽  
Reaction Proceeds

Bicyclic aziridines undergo formal [3+3] ring expansion reactions when exposed to rhodium-bound vinyl carbenes to form complex dehydropiperidines in a highly stereocontrolled rearrangement. Mechanistic studies and DFT computations indicate the reaction proceeds through the formation of a vinyl aziridinium ylide; this reactive intermediate undergoes a concerted, asynchronous, pseudo-[1,4]- sigmatropic rearrangement to directly furnish the heterocyclic products with net retention at the new C-C bond. In combination with an asymmetric silver-catalyzed aziridination developed in our group, this method quickly delivers enantioenriched scaffolds with up to three contiguous stereocenters. The mild reaction conditions, functional group tolerance, and high stereochemical retention of this method are especially well-suited for appending piperidine motifs to natural product and complex molecules. Ultimately, our work establishes the value of underutilized aziridinium ylides as key intermediates in strategies to convert small, strained rings to larger N-heterocycles.

2,3-Sigmatropic Rearrangement of Sulfonium Ylides Generated by Addition of Samarium Carbenoids

Synlett ◽  
1998 ◽  
Vol 1998 (12) ◽  
pp. 1366-1368 ◽  
Author(s):  
Munetaka Kunishima ◽  
Daisuke Nakata ◽  
Chikako Goto ◽  
Kazuhito Hioki ◽  
Shohei Tani
Keyword(s):  
Sigmatropic Rearrangement ◽  
Sulfonium Ylides

Stereochemistry of ring enlargement by [2,3] sigmatropic rearrangement of cyclic sulfonium ylides. Synthesis of 5-methylthiacycloalk-4-enes

1979 ◽  
Vol 44 (23) ◽  
pp. 4128-4135 ◽  
Author(s):  
Vanda Cere ◽  
Claudio Paolucci ◽  
Salvatore Pollicino ◽  
Edda Sandri ◽  
Antonino Fava
Keyword(s):  
Sigmatropic Rearrangement ◽  
Ring Enlargement ◽  
Sulfonium Ylides

scholarly journals Sequential cycloaddition and ring expansion reaction of arynes and methylenebenzothiopheneones: synthesis of a benzo-fused eight-membered ring via sulfonium ylides

RSC Advances ◽  
2019 ◽  
Vol 9 (67) ◽  
pp. 39119-39123 ◽  
Author(s):  
Peng Xiao ◽  
Shikuan Su ◽  
Wei Wang ◽  
Weiguo Cao ◽  
Jie Chen ◽  
...  
Keyword(s):  
Ring Expansion ◽  
Membered Ring ◽  
Efficient Construction ◽  
Ring Expansion Reaction ◽  
Sulfonium Ylides ◽  
Reaction Profile

Efficient construction of benzo-fused eight-membered ring containing sulfur. New reaction profile with sulfonium ylides.

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