Fischer Carbene Complexes in Organic Synthesis: Metal-Assisted and Metal-Templated Reactions

Dötz, Karl Heinz; Stendel, Joachim

doi:10.1021/cr900034e

Cited by 319 publications

(110 citation statements)

References 605 publications

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“…The reactivity of Fischer carbene complexes containing α,β-unsaturated carbon substituents with a variety of organic substrates have been thoroughly investigated and extensively reviewed [1][2][3][4][5][6][7][8][9][10][11][84][85][86][87]. Well-known classes of monocarbene complexes used as precursors in organic synthesis via organometallic intermediates are those displaying carbene substituents with a-unsaturated carbon-carbon bonds.…”

Section: Fischer Carbene Complexes With A-alkynyl Substituents (Iv)mentioning

confidence: 99%

“…Well-known classes of monocarbene complexes used as precursors in organic synthesis via organometallic intermediates are those displaying carbene substituents with a-unsaturated carbon-carbon bonds. One of the first examples studied was the Dötz-reaction whereby 1-alkenylcarbene substituents of a group 6 transition metal carbonyl reacts with an alkyne in a [3 + 2] or [3 + 2 + 1] cycloaddition reaction [84]. This reaction has found wide application in organic synthesis.…”

Section: Fischer Carbene Complexes With A-alkynyl Substituents (Iv)mentioning

confidence: 99%

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Recent advances in the field of multicarbene and multimetal carbene complexes of the Fischer-type

Bezuidenhout

Lotz

Liles

et al. 2012

Coordination Chemistry Reviews

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Section: Fischer Carbene Complexes With A-alkynyl Substituents (Iv)mentioning

confidence: 99%

Section: Fischer Carbene Complexes With A-alkynyl Substituents (Iv)mentioning

confidence: 99%

Recent advances in the field of multicarbene and multimetal carbene complexes of the Fischer-type

Bezuidenhout

Lotz

Liles

et al. 2012

Coordination Chemistry Reviews

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“…[5] In these reactions, the produced alkenyltungsten moieties were protonated by the During these studies, we thought of utilizing the alkenyltungsten intermediates for further carbon-carbon bond formation, because these intermediates could be regarded as a anions of tungsten-carbene complexes. [6] We expected that synthetically useful reactions based on the geminal carbofunctionalization strategy might be achieved through appropriate design of the starting materials. We then considered the reaction behavior of the acetylenic dienol silyl ethers 1 (Scheme 4) as substrates.…”

Section: Introductionmentioning

confidence: 99%

“…[11] [ReBr(CO) 5 ] showed moderate activity under heating conditions, but under photoirradiation conditions a very high catalytic activity was achieved ( 6 ] and [ReCl(CO) 5 ] catalyzed the geminal carbo-functionalization reaction very efficiently, the generality of the reaction was examined, and the results are summarized in Table 2. [12] The trisubstituted dienes 1 b-1 d, with a methyl, primary, or secondary alkyl group at their b positions (R 1 ), were cyclized to afford the corresponding bicyclic enol silyl ethers (R 1 -a product major) in good yields ( Table 2, entries 1-3).…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, treatment of the two isomers 6-a and 6-b again with catalytic amounts of [W(CO) 6 ] and with water (3 mol equiv) under photoirradiation conditions in THF gave the tricyclic ketones 7-a and 7-b, each containing a triquinane skeleton, in yields of 52 and 78 %, respectively (Scheme 6a and b). The basic carbon skeleton of triquinanes can thus easily be constructed with the aid of Re-and Wcatalyzed cyclizations.…”

Section: Introductionmentioning

confidence: 99%

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Tungsten(0)‐ and Rhenium(I)‐Catalyzed Tandem Cyclization of Acetylenic Dienol Silyl Ethers Based on Geminal Carbo‐Functionalization of Alkynes

Kusama

Karibe

Imai

et al. 2011

Chemistry A European J

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Tungsten(0)- and rhenium(I)-catalyzed reactions of acetylenic dienol silyl ethers based on the concept of geminal carbo-functionalization of alkynes are reported. Treatment of 3-siloxy-1,3-diene-7-ynes with catalytic amounts of [W(CO)(6)] or [ReCl(CO)(5)] under photoirradiation conditions gives synthetically useful bicyclo[3.3.0]octane derivatives in good yields. Extremely high catalytic activity is noted for the rhenium(I) complex. The reaction has been extended to substrates containing a nitrogen atom in their tethers. In this case, two kinds of synthetically useful heterocyclic compounds-the 2-azabicyclo[3.3.0]octane derivatives 9 and the monocyclic dihydropyrroles 10, with allenyl substituents-are obtained, and selective preparation of either product can be achieved through the use of an appropriate combination of the nitrogen substituent and the type of the rhenium(I) catalyst. The 2-azabicyclo[3.3.0]octane derivatives 9 are obtained selectively by carrying out treatment of N-Ns derivatives in the presence of [ReCl(CO)(4)(PPh(3))], whereas the dihydropyrrole derivatives 10 are obtained by treatment of N-Mbs derivatives with [ReCl(CO)(5)]/AgSbF(6) . Finally, we have applied this geminal carbo-functionalization to one-carbon-elongated substrates containing N-Ts moieties in their tethers. Selective 5-exo cyclization is achieved in the presence of gold(I) or rhenium(I) catalysts, whereas 6-endo cyclization is observed on use of [W(CO)(6)].

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Catalytic, Asymmetric, Intramolecular Carbon–Hydrogen Insertion

2012

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The insertion of a chiral‐ligated metal carbene into an aliphatic C‐H bond to construct a carbon‐carbon bond imparts asymmetry into the resultant molecule to form enantiomerically enriched lactones, lactams, and cycloalkane derivatives and returns the chiral‐ligated metal to its catalytically active state. Insertion is favored by electron‐donating groups adjacent to the C‐H bond that undergoes insertion, and is disfavored by electron‐withdrawing groups. Chiral dirhodium(II) carboxamidates have proven to have the greatest breadth of high selectivities, but other classes of catalysts are selective in specific cases. Although there are examples of iodonium ylides as reactants, diazo compounds are the reactants of choice for these reactions. Diazocarbonyl compounds, especially diazoacetates and diazoacetamides, have reactivities and selectivities that are most suitable for high product yields and high stereoselectivities. This reaction is optimally designed for the formation of five‐membered ring compounds using diazoacetates and diazoacetamides and of four‐membered ring products with constrained diazoacetamides. Access to lignan lactones, baclofen, deoxyxylolactone, and rolipram, among others, exemplify the efficiencies of this methodology relative to other synthetic approaches.

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Fischer Carbene Complexes in Organic Synthesis: Metal-Assisted and Metal-Templated Reactions

Cited by 319 publications

References 605 publications

Recent advances in the field of multicarbene and multimetal carbene complexes of the Fischer-type

Recent advances in the field of multicarbene and multimetal carbene complexes of the Fischer-type

Tungsten(0)‐ and Rhenium(I)‐Catalyzed Tandem Cyclization of Acetylenic Dienol Silyl Ethers Based on Geminal Carbo‐Functionalization of Alkynes

Catalytic, Asymmetric, Intramolecular Carbon–Hydrogen Insertion

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