21336-06-1Relevant articles and documents
Transition-Metal Catalysis of Triene 6π Electrocyclization: The π-Complexation Strategy Realized
Baldridge, Kim K.,Chen, Jiyue,Li, Yifan,O'Connor, Joseph M.,Qin, Pengjin,Rheingold, Arnold L.,Tufekci, Burak,Wang, Li-An
, p. 17958 - 17965 (2020)
Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally
Unlocking acyclic π–bond rich structure space with tetraethynylethylene–tetravinylethylene hybrids
Horvath, Kelsey L.,Magann, Nicholas L.,Sowden, Madison J.,Gardiner, Michael G.,Sherburn, Michael S.
, p. 19746 - 19753 (2019/12/25)
Literature reports describe tetraethynylethylene (TEE) as unstable but tetravinylethylene (TVE) as stable. The stabilities of these two known compounds are reinvestigated, along with those of five unprecedented TEE-TVE hybrid compounds. The five new C10 hydrocarbons possess a core, tetrasubstituted C=C bond carrying all possible combinations of vinyl and ethynyl groups. A unified strategy is described for their synthesis, whereupon cross-conjugated ketones are dibromo-olefinated then cross-coupled. Due to an incorrect but nonetheless widely held belief that acyclic π-bond rich hydrocarbons are inherently unstable, a standardized set of robustness tests is introduced. Whereas only TVE survives storage in neat form, all seven hydrocarbons are remarkably robust in dilute solution, generally surviving exposure to moderate heat, light, air, and acid. The first X-ray crystal structure of TEE is reported. Subgroups of hybrids based upon conformational preferences are identified through electronic absorption spectra and associated computational studies. These new acyclic π-bond rich systems have extensive, untapped potential for the production of stable, conjugated carbon-rich materials.
Gold-catalyzed hydroarylating cyclization of 1,2-Bis(2-iodoethynyl)benzenes
N?sel, Pascal,Müller, Vanessa,Mader, Steffen,Moghimi, Setareh,Rudolph, Matthias,Braun, Ingo,Rominger, Frank,Hashmi, A. Stephen K.
supporting information, p. 500 - 506 (2015/03/05)
1,5-Diynes bearing halogen-substituted alkynes were synthesized and converted in the presence of a gold catalyst. In contrast to the corresponding hydroarylating aromatization reaction with terminal alkynes, a totally different reaction mode was observed.
Novel chemistry of α-tosyloxy ketones: Applications to the solution- and solid-phase synthesis of privileged heterocycle and enediyne libraries
Nicolaou,Montagnon,Ulven,Baran,Zhong,Sarabiat
, p. 5718 - 5728 (2007/10/03)
New synthetic technologies for the preparation and elaboration of α-tosyloxy ketones in solution and on solid-phase are described. Both olefins and ketones serve as precursors to these relatively stable chemical entities: olefins via a novel one-pot epoxi
Photochemical cycloaromatization of non-benzenoid enediynes
Kaneko,Kaneko, Toshio,Takahashi,Takahashi, Miki,Hirama,Hirama, Masahiro
, p. 1267 - 1268 (2007/10/03)
An efficient photo-Bergman reaction of aliphatic enediynes has been realized. Photolysis of 1 results in the formation of 4 in good yields along with [D2]3. Enediyne 4, which has never been isolated in the thermal reaction of 1, arises here by a retro-Bergman reaction of the diradical intermediate 2.
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
