Carbene, 17: Die thermische Isomerisierung von 8‐Phenylbicyclo[5.1.0]octa‐2,4‐dienen

Maas, Gerhard; Regitz, Manfred

doi:10.1002/cber.19781110509

Cited by 9 publications

(3 citation statements)

References 43 publications

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“…[595] Reaction with water, alcohols and amines leads to phosphinic acids (843, X ϭ OH), phoshinates (843, X ϭ OR) and phosphinamides (843, X ϭ NR 2 ), respectively. [596] The intervening carbenes 845 are also trapped by nucleophiles (Ǟ 842), alkenes (Ǟ 847), [597] and arenes, [598] sometimes to the exclusion of PǞC shifts. The influence of R and Ar on the competing rearrangement and OϪH insertion of 845 is illustrated in Table 11.…”

Section: α-Diazophosphane Oxides -Phosphinates and Related Substratesmentioning

confidence: 99%

100 Years of the Wolff Rearrangement

2002

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The conversion of α‐diazo ketones into ketenes, and products derived therefrom, was discovered by Wolff in 1902. Major applications of the Wolff rearrangement, such as the Arndt−Eistert reaction (homologation of carboxylic acids) and the ring contraction of cyclic ketones, have been with us for some while. Nevertheless, substantial progress has been made recently. The reaction mechanism has been explored by means of matrix isolation, time‐resolved spectroscopy, and computation. Full retention of configuration of the migrating group has been established by using enantioselective chromatography. The Arndt−Eistert reaction has witnessed a renaissance in the field of natural products, in particular β‐amino acids and β‐peptides. Ring‐contracting Wolff rearrangements and ketene cycloadditions have been applied in syntheses of increasingly complex, biologically active target molecules. These accomplishments, as well as unsolved problems, are addressed in the present review. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Section: α-Diazophosphane Oxides -Phosphinates and Related Substratesmentioning

confidence: 99%

100 Years of the Wolff Rearrangement

2002

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“…166,167,168 In this type of transformation the use of transition-metal-catalysts, including copper-, rhodium-and ruthenium-catalyst, has represented the method of choice for generating the corresponding reactive species, although some examples employing photochemicalinduced nitrogen elimination have to be also cited. 27,[169][170][171]172 High diastereo-and enantio-control have been demonstrated by the use of a number of chiral transition metal complexes, rhodium-and ruthenium-based catalysts, in particular. However, the possibility to direct the reaction toward the preferential formation of the cis isomer still remains unsuccessful.…”

Section: Cyclopropanation Reactionsmentioning

confidence: 99%

“…The cyclopropanation of alkene bonds is one of the most investigated areas in PCDC chemistry. It does not sound surprising because the cyclopropane ring is an important structural motif in biologically active compounds, , as well as a versatile building block able to be converted into a range of other functionalities. − In this type of transformation, the use of transition-metal catalysts, including copper-, rhodium-, and ruthenium-catalyst, has represented the method of choice for generating the corresponding reactive species, although some examples employing photochemical-induced nitrogen elimination have also to be cited. ,− High diastereo- and enantio-control have been achieved by the use of a number of chiral transition metal complexes, rhodium- and ruthenium-based catalysts, in particular. However, the possibility to direct the reaction toward the preferential formation of the cis isomer remains unsuccessful.…”

Section: Chemistry Of λ5-phosphorus-containing α-Diazo Compoundsmentioning

confidence: 99%

λ⁵-Phosphorus-Containing α-Diazo Compounds: A Valuable Tool for Accessing Phosphorus-Functionalized Molecules

2016

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The compounds characterized by the presence of a λ-phosphorus functionality at the α-position with respect to the diazo moiety, here referred to as λ-phosphorus-containing α-diazo compounds (PCDCs), represent a vast class of extremely versatile reagents in organic chemistry and are particularly useful in the preparation of phosphonate- and phosphinoxide-functionalized molecules. Indeed, thanks to the high reactivity of the diazo moiety, PCDCs can be induced to undergo a wide variety of chemical transformations. Among them are carbon-hydrogen, as well as heteroatom-hydrogen insertion reactions, cyclopropanation, ylide formation, Wolff rearrangement, and cycloaddition reactions. PCDCs can be easily prepared from readily accessible precursors by a variety of different methods, such as diazotization, Bamford-Stevens-type elimination, and diazo transfer reactions. This evidence along with their relative stability and manageability make them appealing tools in organic synthesis. This Review aims to demonstrate the ongoing utility of PCDCs in the modern preparation of different classes of phosphorus-containing compounds, phosphonates, in particular. Furthermore, to address the lack of precedent collective papers, this Review also summarizes the methods for PCDCs preparation.

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Carbenes, 18: Isomerization Reactions of Phosphoryl‐vinyl‐carbenes to Phosphorylated Cyclopropenes, Allenes, Acetylenes, Indenes, and 1,3‐Butadienes

1978

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Carbene, 17: Die thermische Isomerisierung von 8‐Phenylbicyclo[5.1.0]octa‐2,4‐dienen

Cited by 9 publications

References 43 publications

100 Years of the Wolff Rearrangement

100 Years of the Wolff Rearrangement

λ⁵-Phosphorus-Containing α-Diazo Compounds: A Valuable Tool for Accessing Phosphorus-Functionalized Molecules

Carbenes, 18: Isomerization Reactions of Phosphoryl‐vinyl‐carbenes to Phosphorylated Cyclopropenes, Allenes, Acetylenes, Indenes, and 1,3‐Butadienes

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Carbene, 17: Die thermische Isomerisierung von 8‐Phenylbicyclo[5.1.0]octa‐2,4‐dienen

Cited by 9 publications

References 43 publications

100 Years of the Wolff Rearrangement

100 Years of the Wolff Rearrangement

λ5-Phosphorus-Containing α-Diazo Compounds: A Valuable Tool for Accessing Phosphorus-Functionalized Molecules

Carbenes, 18: Isomerization Reactions of Phosphoryl‐vinyl‐carbenes to Phosphorylated Cyclopropenes, Allenes, Acetylenes, Indenes, and 1,3‐Butadienes

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λ⁵-Phosphorus-Containing α-Diazo Compounds: A Valuable Tool for Accessing Phosphorus-Functionalized Molecules