Recent advances of the tandem difunctionalization of alkynes via five kinds of mechanisms

Synthesis ◽  
2021 ◽  
Author(s):  
Biwen Gao ◽  
Danfeng Deng ◽  
Dayun Huang ◽  
Xiangyu Sun

Recent advances of the tandem difunctionalization of alkynes in decade (2010-2020) were summarized via five categories by triggered mechanisms: (1) radical addition and coupling for the synthesis of polysubstituted ketones and alkenes; (2) electrophilic addition of alkynes; (3) haloalkyne or copper acetylide-mediated reactions; (4) preparation of cyclic compounds via radical process, palladium-catalyzed reactions or conjugate addition; (5) cyclic compounds as intermediates in ring openings. Herein, radical, electrophilic and nucleophilic reactions were well discussed. We hope this review will promote future research in this area.

2012 ◽  
Vol 31 (9) ◽  
pp. 3492-3498 ◽  
Author(s):  
Akinobu Naka ◽  
Joji Ohshita ◽  
Eigo Miyazaki ◽  
Toshiko Miura ◽  
Hisayoshi Kobayashi ◽  
...  

2009 ◽  
Vol 64 (11-12) ◽  
pp. 1580-1590 ◽  
Author(s):  
Akinobu Naka ◽  
Jun Sakata ◽  
Junnai Ikadai ◽  
Hiroyuki Kawasaki ◽  
Joji Ohshita ◽  
...  

The synthesis and palladium-catalyzed reactions of cis- and trans-3,4-benzo-1,2-diisopropyl- 1,2-dimethyl-1,2-disilacyclobut-3-ene (1a and 1b) are reported. Their reactions with diphenylacetylene in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium(0) proceeded with high stereospecificity to give cis- and trans-5,6-benzo-1,4-diisopropyl-1,4-dimethyl- 2,3-diphenyl-1,4-disilacyclohexa-2,5-diene, 2a and 2b, in 95% and 93% yield, respectively. Similar palladium-catalyzed reactions of 1a and 1b with monosubstituted acetylenes, such as 1-hexyne, tert-butylacetylene, phenylacetylene, and trimethylsilylacetylene, also proceeded stereospecifically to afford the respective cis- and trans-5,6-benzo-1,4-disilacyclohexa-2,5-dienes, 3a - 6a and 3b - 6b, in excellent yields and as the sole products. The palladium-catalyzed reaction of 1a with styrene gave a mixture consisting of two stereoisomers, cis-2- and trans-2-phenyl-substituted 5,6- benzo-(r-1),cis-4-diisopropyl-1,4-disilacyclohex-5-ene 7a and 8a in a ratio of 5 : 3 in 72% combined yield, while the reaction of styrene with 1b afforded two stereoisomers, 7b and 8b, in a ratio of 2 : 1 in 80% combined yield. With 1-hexene, 1a gave two stereoisomers, 5,6-benzo-cis-2-(nbutyl)-( r-1),cis-4-diisopropyl- and 5,6-benzo-trans-2-(n-butyl)-(r-1),cis-4-diisopropyl-1,4-dimethyl- 1,4-disilacyclohex-5-ene, 9a and 10a, in a ratio of 1 : 1 in 70% combined yield. A similar reaction of 1b with 1-hexene produced 5,6-benzo-cis-2-(n-butyl)-(r-1),trans-4-diisopropyl-1,4-dimethyl-1,4- disilacyclohex-5-ene in 81% yield and as a single isomer


2007 ◽  
Vol 88 (6) ◽  
pp. 1643-1655 ◽  
Author(s):  
Jeanmarie Verchot-Lubicz ◽  
Chang-Ming Ye ◽  
Devinka Bamunusinghe

Recent advances in potexvirus research have produced new models describing virus replication, cell-to-cell movement, encapsidation, R gene-mediated resistance and gene silencing. Interactions between distant RNA elements are a central theme in potexvirus replication. The 5′ non-translated region (NTR) regulates genomic and subgenomic RNA synthesis and encapsidation, as well as virus plasmodesmal transport. The 3′ NTR regulates both plus- and minus-strand RNA synthesis. How the triple gene-block proteins interact for virus movement is still elusive. As the potato virus X (PVX) TGBp1 protein gates plasmodesmata, regulates virus translation and is a suppressor of RNA silencing, further research is needed to determine how these properties contribute to propelling virus through the plasmodesmata. Specifically, TGBp1 suppressor activity is required for virus movement, but how the silencing machinery relates to plasmodesmata is not known. The TGBp2 and TGBp3 proteins are endoplasmic reticulum (ER)-associated proteins required for virus movement. TGBp2 associates with ER-derived vesicles that traffic along the actin network. Future research will determine whether the virus-induced vesicles are cytopathic structures regulating events along the ER or are vehicles carrying virus to the plasmodesmata for transfer into neighbouring cells. Efforts to assemble virions in vitro identified a single-tailed particle (STP) comprising RNA, coat protein (CP) and TGBp1. It has been proposed that TGBp1 aids in transport of virions or STP between cells and ensures translation of RNA in the receiving cells. PVX is also a tool for studying Avr–R gene interactions and gene silencing in plants. The PVX CP is the elicitor for the Rx gene. Recent reports of the PVX CP reveal how CP interacts with the Rx gene product.


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