Stereoselective [3+2+2] cycloaddition utilizing optically active binuclear Fischer carbene complexes with alkynes

Kamikawa, Ken; Shimizu, Yasunori; Matsuzaka, Hiroyuki; Uemura, Mamoru

doi:10.1016/j.jorganchem.2005.07.089

Cited by 19 publications

(8 citation statements)

References 30 publications

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“…Compound 15 is only observed when R is a methoxy substituent on Fischer carbene 12 and trimethylsilylacetylene is used, leading to 14 and 15 in 27 % yield. In some cases, the product undergoes a mono‐demetalation to give 16 in 10–25 % yield [94] …”

Section: Fischer Carbene Complexes With Metal‐mediated Higher‐order Cycloadditionsmentioning

confidence: 99%

Fischer Carbene Complexes: A Glance at Two Decades of Research on Higher‐Order Cycloaddition Reactions

Feliciano

Vázquez

Benítez‐Puebla

et al. 2021

Chemistry A European J

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The structure of Fischer carbene complexes (FCCs) is electron deficient. If bearing an α,β‐unsaturated system, it can generate a wide variety of compounds by undergoing many different transformations, including higher‐order cycloadditions. The latter are described as pericyclic reactions in which more than six electrons participate. These reactions have been employed in various areas of organic synthesis, resulting in highly selective compounds with a broad range of scaffolds. The first studies on higher‐order cycloadditions involving FCCs frequently yielded competing byproducts. Many groups have attempted to increase selectivity by exploring distinct reaction conditions, reagents and co‐catalysts (e. g., metal‐mediated cycloadditions). The present review is the first to focus exclusively on using higher‐order cycloadditions involving FCCs to synthesize carbocycles and heterocycles. Based on two decades of reports, an analysis is made of the main aspects of the mechanisms proposed for higher‐order cycloadditions and the structural diversity obtained by the substituent effect.

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Section: Fischer Carbene Complexes With Metal‐mediated Higher‐order Cycloadditionsmentioning

confidence: 99%

Fischer Carbene Complexes: A Glance at Two Decades of Research on Higher‐Order Cycloaddition Reactions

Feliciano

Vázquez

Benítez‐Puebla

et al. 2021

Chemistry A European J

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“…In an another report, Kamikawa and co‐workers describe the [3+2+2] cycloadditions of optically active α,β‐unsaturated binuclear Fischer carbene complexes with different substituted terminal alkynes in the presence of Ni(COD) 2 as catalyst for the formation of planar chiral cycloheptatrienes (Scheme ) . The [3+2+2] cycloadditions of binuclear Fischer‐carbene complexes with 1‐pentyne 12a (3.0 equiv.)…”

Section: Nickel‐catalyzed [3+2+2] Cycloaddition Reactionsmentioning

confidence: 99%

“…The[3+2+2] cycloadditions reaction of Fischer‐carbene complexes 11a with aromatic alkyne such as phenylacetylene 12b have led to the formation of two different [3+2+2] cycloadducts, heptatriene chromium complex 13ab (with high diastereoselectivity) and chromium‐free product 15ab with 28 % and 25 % yields respectively. The [3+2+2] cycloadditions of α,β‐unsaturated binuclear Fischer‐carbene complexes 11a – d with trimethylsilyl acetylene 12c afford a diastereomeric mixture of 13ac / 14ac along with chromium‐free cycloadduct 15ac …”

Section: Nickel‐catalyzed [3+2+2] Cycloaddition Reactionsmentioning

confidence: 99%

Transition‐Metal‐Catalyzed [3+2+2] Cycloaddition Reactions

et al. 2017

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[3+2+2] Cycloaddition reactions are of key importance in organic chemistry for the synthesis of seven‐membered mono‐ and condensed carbocycles. This review article summarises the different reports on transition‐metal‐catalysed [3+2+2] cycloaddition reactions since 2000. Different transition‐metals, such as Ni, Rh, Pd, Co, or Ru, which have been earlier reported for higher order [3+2+2] cycloaddition reactions are summarized in this article. The [3+2+2] cycloadditions of different functionalized substrates afford cycloheptane derivatives, 6–7,5–7 condensed bicyclic carbocycles, or 5–7–5 or 6–7–5 condensed tricyclic carbocycles. These higher order cycloaddition reactions may provide an easy route for the total synthesis of natural products, or as a preferable key synthetic step leading to final structure.

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“…20 Taking advantage of this fact, Kamikawa has prepared optically pure planar chiral cycloheptatriene chromium complexes 50 and 51 by the diastereoselective [3+2+2] cycloaddition, employing binuclear a,b-unsaturated FCCs 49 (Scheme 12). 21 Further functionalization of both chromium-coordinated rings at 50 could be stereo-and chemoselectively achieved by utilizing the distinct properties of the chromium complexes. Planar chiral ferrocenyl carbene complex 52 also has partaken in this reaction leading to the corresponding adduct 53 as a single diastereomer in 60% yield.…”

Section: Reactions With Enediynes the Reaction Of Fccs 1cmentioning

confidence: 99%

Multi-component reactions involving group 6 Fischer carbene complexes: a source of inspiration for future catalytic transformations

2010

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The ability of heteroatom stabilized Fischer carbene complexes (FCCs) to participate in multicomponent reactions (MCRs) has become a characteristic of such organometallics, particularly of chromium carbenes. This feature article updates the main results in this field during the last lustrum, highlighting the ability of FCCs for the construction of densely functionalized frameworks, mainly through the successive incorporation of unsaturated moieties (alkynes, CO ligands,. . .) in a sequential manner. Examples where up to seven components are coupled will be presented.

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Stereoselective [3+2+2] cycloaddition utilizing optically active binuclear Fischer carbene complexes with alkynes

Cited by 19 publications

References 30 publications

Fischer Carbene Complexes: A Glance at Two Decades of Research on Higher‐Order Cycloaddition Reactions

Fischer Carbene Complexes: A Glance at Two Decades of Research on Higher‐Order Cycloaddition Reactions

Transition‐Metal‐Catalyzed [3+2+2] Cycloaddition Reactions

Multi-component reactions involving group 6 Fischer carbene complexes: a source of inspiration for future catalytic transformations

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