Silicon-Oxygen Heterocycles from Thermal, Photochemical, and Transition-Metal-Catalyzed Decomposition of α-(Alkoxysilyl and Alkenyloxysilyl)-α-diazoacetates

Maas, Gerhard; Krebs, Fred C.; Werle, Thorsten; Gettwert, Volker; Striegler, Ruth

doi:10.1002/(sici)1099-0690(199908)1999:8<1939::aid-ejoc1939>3.3.co;2-1

Cited by 5 publications

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“…Reasonable yields were only obtained when the stationary concentration of the diazo compound was achieved and 254 nm monochromatic light used as irradiation source (Scheme 45). [125]…”

Section: Scheme 44mentioning

confidence: 99%

Developments in the Photochemistry of Diazo Compounds

Candeias¹,

Afonso

2009

COC

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This review focus on photolytic reactions of diazo compounds, covering mainly synthetic applications such as Wolff rearrangement, 1,2-shift, X-H insertion, cyclopropanation, hydrogen abstraction and reaction with oxygen and physical organic studies, with special relevance to mechanistic considerations. the synthesis of a diazo compound if loss of a proton from the C()-atom of the primarily formed alkanediazonium ion is faster than the loss of dinitrogen, which makes this method almost specific for the case of aliphatic amines containing a C()-atom substituted by an acidifying group. Diazo compounds can also be prepared by acylation or cleavage of aliphatic diazo compounds containing the structural requirements. For instance, diazo carbonyl carbamate 4 can be prepared through the reaction of the carboxylate precursor with a chloroformate and further reaction of the anhydride with diazomethane (Scheme 2).[13] Making use of oxidants, diazo carbonyl compounds can be prepared by hydrazone oxidation in the presence of mercury oxide and potassium hydroxide.[14] Scheme 1 Scheme 2 Diazo-transfer reactions have been widely used since they are a more general method for the preparation of diazo compounds. In this reaction, the diazo moiety is transferred from the donor to an acceptor where the donor is a sulphonyl azide (6) and the acceptor a carbanion formed after deprotonation (Scheme 3).[3,15] Scheme 3 Diazo compounds can be submitted to several reaction conditions and myriads of compounds can be obtained by the proper choice of conditions and reagents. In the absence of a metal catalyst, this decomposition can be induced by thermolysis or photolysis, generating a highly reactive intermediate species that, in most cases, affords a complex mixture of products. Depending on the diazo compound and the reaction conditions, the resulting products can be derived from C-H or X-H

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“…Reasonable yields were only obtained when the stationary concentration of the diazo compound was achieved and 254 nm monochromatic light used as irradiation source (Scheme 45). [125]…”

Section: Scheme 44mentioning

confidence: 99%

Developments in the Photochemistry of Diazo Compounds

Candeias¹,

Afonso

2009

COC

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“…Polymorphism is recognized as being a vital branch of solid-state supramolecular chemistry. The direct photolysis of a-(alkenyloxy)silyl-substituted diazoacetate 76a leads to a carbene, which undergoes an intramolecular [2 þ 1] cycloaddition with the terminal alkene to afford 77a in 55% yield (Scheme 4.35) [55]. An a-alkenysilyl-substituted diazoacetate 76b also leads to 77b in 68% yield (Scheme 4.35) upon direct irradiation [56].…”

Section: Oxa-di-p-methane Rearrangement Of Bg-unsaturated Ketones Anmentioning

confidence: 99%

Formation of a Three‐Membered Ring

Tsuno

2009

Handbook of Synthetic Photochemistry

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“…Intramolecular carbene and metal-carbene reactions of appropriately functionalized diazo compounds allow the ready construction of a broad range of carbo-and heterocyclic rings. [1][2][3][4][5] Starting from silyldiazoalkanes and silyldiazoacetates, this strategy gives access to various silaheterocycles 6 mainly by C,H insertion, [7][8][9][10] intramolecular cyclopropanation, 10 and reaction at a C•C bond. 11 Successful intramolecular cyclopropanation reactions with allyloxysilyl-and [(3-butenyl)oxysilyl]-diazoacetates 10 led us to wonder whether the tether between the two reacting functionalities could be shortened by one member, i.e.…”

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confidence: 99%