143192-60-3Relevant articles and documents
Enantioselective Rh(II)-Catalyzed Desymmetric Cycloisomerization of Diynes: Constructing Furan-Fused Dihydropiperidines with an Alkyne-Substituted Aza-Quaternary Stereocenter
Cao, Tongxiang,Chen, Kai,Lu, Jiajun,Ma, Jun,Wu, Rui,Zhu, Shifa
supporting information, p. 14916 - 14925 (2021/09/18)
Described herein is an enantioselective dirhodium(II)-catalyzed cycloisomerization of diynes achieved by the strategy of desymmetrization, which not only represents a new cycloisomerization reaction of diynes but also constitutes the first Rh(II)-catalyzed asymmetric intramolecular cycloisomerization of 1,6-diynes. This protocol provides a range of valuable furan-fused dihydropiperidine derivatives with an enantiomerically enriched alkynyl-substituted aza-quaternary stereocenter in high efficiency, complete atom economy, and excellent enantioselectivity (up to 98% ee). Besides, the highly functionalized products could be easily transformed into various synthetically useful building blocks and conjugated with a series of pharmaceutical molecules. The mechanism involving a concerted [3+2] cycloaddition/[1,2]-H shift of the Rh(II) carbenoid intermediate was elucidated by DFT calculations and mechanistic studies. More importantly, the first single crystal of alkyne-dirhodium(II) was obtained to show that a η2-coordinating activation of alkynal by dirhodium(II) was involved. Weak hydrogen bondings between the carboxylate ligands and alkynal were found, which probably made the well-defined paddlewheel-like dirhodium(II) distinctive from other metal complexes in catalyzing this transformation. Furthermore, the origin of the enantioselectivity was elucidated by a Rh2(R-PTAD)4-alkyne complex and additional calculational studies.
Synthesis of Naphthalenyl Triflates via the Cationic Annulation of Benzodiynes with Triflic Acid
Ge, Chenxin,Wang, Guohua,Wu, Panpan,Chen, Chao
supporting information, p. 5010 - 5014 (2019/07/08)
A highly efficient and regioselective annulation of benzodiynes promoted by triflic acid has been developed. This protocol provides a step and atom-economic access to a series of naphthalenyl triflates. Furthermore, direct synthetic applications of this r
The Gold(I)-Mediated Domino Reaction to Fused Diphenyl Phosphoniumfluorenes: Mechanistic Consequences for Gold-Catalyzed Hydroarylations and Application in Solar Cells
Arndt, Sebastian,Borstelmann, Jan,Eshagh Saatlo, Rebeka,Antoni, Patrick W.,Rominger, Frank,Rudolph, Matthias,An, Qingzhi,Vaynzof, Yana,Hashmi, A. Stephen K.
supporting information, p. 7882 - 7889 (2018/06/15)
A domino sequence, involving a phosphinoauration and a gold-catalyzed 6-endo-dig cyclization step, was developed. Starting from modular and simple-to-prepare phosphadiynes, π-extended phosphoniumfluorenes were synthesized. The mechanistic proposal was sup
