Furanosylidene and Iminofuranosylidene Complexes: Synthesis by Stoichiometric Olefin Metathesis and Ring-Opening/Mitsunobu-Recyclization Sequence

Haase, Wilm‐Christian; Nieger, Martin; Dötz, Karl Heinz

doi:10.1002/(sici)1521-3765(19990702)5:7<2014::aid-chem2014>3.0.co;2-n

Cited by 25 publications

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References 22 publications

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“…Given the isolobal relationship between Fischer carbenes and esters, we envisioned these complexes could exhibit polymerization tendencies reminiscent of common ester-containing monomers. In light of this, as well as the established compatibility between Fischer carbenes and metathesis catalysts, , we pursued ring opening metathesis polymerization (ROMP) as a strategy for accessing metallocarbene-containing polymers (Scheme ).…”

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Synthesis and Reactivity of Metallocarbene-Containing Polymers

Wilson

Brantley

2019

J. Am. Chem. Soc.

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Metallopolymers are an emerging class of materials with potential utility as semiconductors, catalysts, optical device components, and stimuli responsive networks. While polymer frameworks have been decorated with an array of organometallic moieties, the incorporation of metallocarbenes has been largely overlooked. Here, we report ring-opening metathesis polymerization as a strategy for the synthesis of Fischer carbenecontaining polymers. High degrees of polymerization were observed (>800 repeats), and the isolated materials exhibited exceptional solubility and thermal stability. The tungsten carbene subunits were readily incorporated into block copolymers and could be modified through subsequent transformations. Moreover, the metallocarbene polymers were found to release carbon monoxide upon exposure to light or oxygen, which is unusual for tungsten carbene complexes. These metallocarbenecontaining polymers could represent new platforms for the development of functional materials.

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Synthesis and Reactivity of Metallocarbene-Containing Polymers

Wilson

Brantley

2019

J. Am. Chem. Soc.

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“…The cyclization of aminocarbene complexes 48 was conducted in the presence of PPh 3 and DEAD, and the azacyclopentylidene complexes were isolated with good yields. This approach was used in the synthesis of the iminofuranosylidene complexes 49 and 50 [50].…”

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The Mitsunobu reaction in the chemistry of nitrogen-containing heterocyclic compounds. The formation of heterocyclic systems (review)

Голанцов

Карчава

Yurovskaya

2008

Chem Heterocycl Comp

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Methods for the design of nitrogen-containing heterocyclic systems involving the formation of C-N bonds under the conditions of the Mitsunobu reaction are discussed.The Mitsunobu reaction [1][2][3][4] is the reaction of compounds containing a mobile hydrogen atom HX with alcohols in the presence of a reagent system consisting of an azodicarboxylic ester and a phosphine PR 1 3 . This reaction results in the formation of an alkylation product RX accompanied by oxidation of the phosphine PR 1 3 to phosphine oxide R 1 3 P=O and reduction of the azodicarboxylic ester to the corresponding hydrazine.The reaction takes place under very mild conditions and usually at room temperature. If a chiral secondary alcohol ROH is used, the reaction is usually stereospecific and is accompanied by inversion of the configuration at the asymmetric carbon atom of the alcohol [1-3].From the moment of the first report [5] the Mitsunobu reaction became a powerful tool in synthetic organic chemistry and found widespread use in the synthesis of various heterocyclic compounds, optically active substances, steroids, alkaloids, carbohydrates, and nucleosides [1][2][3][4]6]. In particular, in a number of cases the Mitsunobu reaction has made it possible to synthesize new physiologically active compounds or to put forward new highly effective approaches to synthesis. Several reviews have been devoted to the Mitsunobu reaction [1-4, 6, 7]. Data on the use of the Mitsunobu reaction in the synthesis of alkaloids were reviewed in [6]. Various experimental techniques that make it possible to simplify the isolation of the products of the Mitsunobu reaction RX from the reaction mixture, including the use of reagents attached to a polymer support, were discussed in [7]. _______ * Dedicated to Afanasi Andreevich Akhrem on his 95th birthday. _________________________________________________________________________________________

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