21390-02-3Relevant articles and documents
A convenient synthesis of ethano-bridged cyclic diynes - preparation of 1,1,2,2-tetramethyl-1 ,2-disilacycloocta-3,7-diyne
Haberhauer, Gebhard,Roers, Rolf,Gleiter, Rolf
, p. 8679 - 8682 (1997)
Cyclic diynes bridged by an ethano moiety on one side are formed in the reaction of α,ω-dihalogen precursors with lithium in presence of biphenyl.
Halo-enediynes: Probing the electronic and stereoelectronic contributions to the Bergman cycloaromatization
Plourde II, Gary W.,Warner, Philip M.,Parrish, Dennis A.,Jones, Graham B.
, p. 5369 - 5374 (2002)
A series of halogen-substituted cyclic enediynes were prepared with use of carbenoid coupling strategy. DFT analysis, initially used to identify synthesis candidates, was also employed to rationalize the propensity for cycloaromatization of the compounds. In all cases studied the halogen atom had a strongly retardative effect on the thermal Bergman cycloaromatization reaction. The isolation of the first C-9 monochloroenediyne is noteworthy, and may find application in prodrug design.
Radical reactions of the cobalt-complexed propargyl acetals: Inter- and intramolecular variants
Melikyan, Gagik G.,Voorhees, Erin,Sepanian, Ruth
, p. 69 - 83 (2014/02/14)
Propargyl acetals are used as a new type of substrate in cobaltocene-induced radical reactions stereodirected by a π-bonded Co 2(CO)6 metal core. The experimental protocol involves treatment of the cobalt-complexed acetals with triflic anhydride, an in situ generation of ionic propargyl triflates, and a single-electron, low-temperature reduction of α-alkoxy-stabilized, Co2(CO)6-complexed propargyl cations. Inter- and intramolecular reactions provide a facile access to polyfunctional, topologically diverse 3,4-dialkoxy-1,5-alkadiynes and 3,4-dialkoxy-1,5-cyclodecadiynes with a predominant formation of the respective d,l-diastereomers (73-100% d,l). The stereo- and chemoselectivities are found to be dependent upon the (1) bulkiness of the gamma substituent (1,3-steric induction; d,l- 73-100%), (2) presence of a phosphorus ligand altering the π-bonded metal core (axial ligand induction; d,l- 91-97%), and (3) steric hindrance created by an alpha alkoxy group (1,1-steric induction; d,l- 83-92%).
Ruthenium-catalyzed cycloisomerizations of diynols
Trost, Barry M.,Rudd, Michael T.
, p. 4763 - 4776 (2007/10/03)
A wide variety of diynols containing tertiary, secondary, and primary propargylic alcohols undergo a cycloisomerization reaction to form dienones and dienals in the presence of a catalytic amount of [CpRu(CH3CN) 3]PF6. The
A direct route to conjugated enediynes from dipropargylic sulfones by a modified one-flask Ramberg-Baecklund reaction
Cao, Xiaoping,Yang, Yuying,Wang, Xiaolong
, p. 2485 - 2489 (2007/10/03)
The reaction of dipropargylic sulfones with dibromodifluoromethane in the presence of alumina-supported KOH in dichloromethane solution results in facile rearrangement affording the corresponding conjugated linear and cyclic enediynes in good yields. This result shows that the direct transformation of a- and a′-hydrogen bearing sulfones assembles enediyne units without resorting to the prior preparation of the a-halo sulfone precursors in a separate step.
A direct and stereocontrolled route to conjugated enediynes
Jones, Graham B.,Wright, Justin M.,Plourde, Gary W.,Hynd, George,Huber, Robert S.,Mathews, Jude E.
, p. 1937 - 1944 (2007/10/03)
A unified synthetic route to 3-hex-en-1,5-diynes, a key building block found in many of the enediyne antitumor agents and designed materials, was developed. The method, which relies on a carbenoid coupling-elimination strategy is tolerant of a wide range of functionalities, and was applied to the synthesis of a variety of linear and cyclic enediynes. Reaction parameters can be adjusted to control stereoselectivity of the process, producing linear enediynes from 1:12 to >100:1 E:Z ratio, and in the case of cyclic enediynes, giving the exclusively Z C-9, C-10, or C-11 products. Key features of the process are the ready availability of precursors and the mildness and efficiency of the reaction. Application of the process in the design of materials precursors and preparation of enediyne antitumor agents are presented.
Process for synthesizing enediynes
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, (2008/06/13)
A process for synthesizing enediynes is provided. Specifically, the formed enediynes contain a hex-3-ene-1,5-diynyl group. Production of the enediynes involves adding a base to a propargylic halide in the presence of a chelating agent, which causes a carb
Synthesis, reaction, and cytotoxicity of novel propargylic sulfones
Dai, Wei-Min,Fong, Kin Chiu
, p. 5613 - 5616 (2007/10/02)
Propargylic sulfones 1 and 2 have been synthesized for their potent interactions with DNA. The crown ether conjugate 8 was also prepared from 1 under carefully established reaction conditions. The synthesized propargylic sulfones 2, 5 and 8 exhibited high
Design, synthesis, and study of simple monocyclic conjugated enediynes. The 10-membered ring enediyne moiety of the enediyne anticancer antibiotics
Nicolaou,Zuccarello,Riemer,Estevez,Dai
, p. 7360 - 7371 (2007/10/02)
Following the discovery of the enediyne anticancer antibiotics, investigations were initiated directed toward the design, synthesis, and study of simple monocyclic conjugated enediynes. In this article the synthesis of the parent 10-membered ring enediyne
Synthesis of Aliphatic Dienedials, ω-Hydroxydienals, ω-Hydroxy-2-alkenals, Vinylketones, an Enon-enal and Aliphatic Dienediones
Iriye, Ryozo,Toya, Tsutomu,Makino, Junji,Aruga, Ryuichi,Doi, Yukio,et al.
, p. 989 - 996 (2007/10/02)
Aliphatic bisenals (1a - n), ω-hydroxydienals (2a - n), ω-hydroxy-2-alkenals (3a - d), vinylketones (4a, b), an enon-enal (4c) and three geometric isomers of aliphatic bisenones (5a - g) were synthesized in order to study the relationship between the structure and microbicidal activity.
