537707-02-1Relevant articles and documents
Synthesizing Molecules with Linear Tricyclic 5/5/5 and 6/5/5 Skeletons via [5 + 2 + 1]/Ene Strategy
Liu, Jing,Zhou, Yi,Zhu, Jiaqi,Yu, Zhi-Xiang
supporting information, p. 7566 - 7570 (2021/10/02)
Report here is the development of a [5 + 2 + 1]/ene strategy for the synthesis of molecules with linear tricyclic 5/5/5 and 6/5/5 skeletons widely found in natural products. The first step of this strategy is applying a Rh-catalyzed [5 + 2 + 1] reaction o
Synthesis of 1-hydrocarbon substituted cyclopropyl silyl ketones
Honda, Mitsunori,Sasaki, Sho,Nishimoto, Tsuyoshi,Koshiro, Hiromoto,Kunimoto, Ko-Ki,Segi, Masahito
, p. 3777 - 3781 (2018/09/21)
The synthesis of cyclopropyl silyl ketones possessing a hydrocarbon group at 1-position of three-membered ring was investigated. The reaction of sulfoxonium ylide with α,β-unsaturated acylsilanes derived from α,β-unsaturated aldehydes did not afford the desired acylsilane derivatives. Instead, the corresponding silyl enol ethers were yielded exclusively. On the other hand, the Corey-Chaykovsky cyclopropanation of α-substituted α,β-unsaturated aldehydes proceeded well to give 1-substituted cyclopropyl aldehydes. The silyl substitution of formyl proton in the obtained aldehydes via umpolung of carbonyl group afforded the target acylsilanes.
Highly selective silylformylation of internal and functionalised alkynes with a cationic dirhodium(II) complex catalyst
Biffis, Andrea,Conte, Luca,Tubaro, Cristina,Basato, Marino,Aronica, Laura Antonella,Cuzzola, Angela,Caporusso, Anna Maria
experimental part, p. 792 - 798 (2010/06/19)
The tetracationic complex [Rh2(MeCN)2(Naft)4](BF4)4 (Naft = μ-1,8-naphthyridine) was found to be an efficient catalyst for the silylformylation of internal and functionalised alkynes to yield useful synthetic intermediates. The complex exhibits an unprecedented chemoselectivity towards alkyne silylformylation instead of simple hydrosilylation, as well as a good stereoselectivity. The catalytic efficiency of the complex is markedly superior compared to that of previously reported catalysts such as [Rh+ C7 H8 BPh4-] or Rh4(CO)12; incidentally, the performance of the latter catalyst was found to vary dramatically with its shelf-life, which indicates that the catalyst evolves with ageing towards other species, most notably higher nuclearity rhodium carbonyl clusters, which are more chemoselective towards silylformylation. Preliminary results on the determination of the catalytically active species in the case of complex [Rh2(MeCN)2(Naft)4](BF4)4 indicate that the complex is reduced in situ to a dirhodium(I) species which maintains the dimeric, lantern-shaped structure.
Silylformylation - Fluoride-assisted aryl migration of acetylenic derivatives in a versatile approach to the synthesis of polyfunctionalised compounds
Aronica, Laura Antonella,Raffa, Patrizio,Valentini, Giulia,Caporusso, Anna Maria,Salvadori, Piero
, p. 1845 - 1851 (2007/10/03)
Polyfunctionalised aldehydes and dihydropyrans are prepared from easily available functionalised 1-alkynes through a two-step silylformylation/aryl migration sequence. The silylformylation process is performed under mild experimental conditions and affords the corresponding β-silylalkenals in high yields. The fluoride-promoted migration step occurs instantaneously with quantitative conversion. The chemo-, regio- and stereoselectivity can be modulated according to the nature and the position of the functional group on the acetylene precursors. When a good leaving group is present in the ω position of the aliphatic chain of the alkyne a cyclisation product is obtained, while α,β-unsaturated aldehydes are generated from propargylic tosylamides. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
Fluoride-Promoted Rearrangement of Organo Silicon Compounds: A New Synthesis of 2-(Arylmethyl)aldehydes from 1-Alkynes
Aronica, Laura Antonella,Raffa, Patrizio,Caporusso, Anna Maria,Salvadori, Piero
, p. 9292 - 9298 (2007/10/03)
A new approach to 2-(arylmethyl)aldehydes 4 based upon a 1,2-anionotropic rearrangement of an aryl group is presented. The synthetic sequence begins with a silylformylation reaction of terminal acetylenes 5 with aryl and heteroaryl silanes 6, followed by treatment of the products (Z)-1 with TBAF. The optimization of the experimental conditions of the fluoride-promoted step is described, together with the synthetic potentialities of the process. A plausible mechanism of the rearrangement reaction is reported that suggests the addition of the fluoride ion to the arylsilicon moiety of β-silylalkenals (Z)-1 and the consequent migration of the aryl group to the adjacent carbon atom. Both aryl and heteroaryl substituents can rearrange without any loss of configuration. Bromofunctionalized substrates undergo an intramolecular reaction that affords exclusively carbacyclobenzyl aldehydes, further enhancing the high synthetic value of this method.
