- METALLORGANISCHE DIAZOALKANE XVI. SYNTHESE VON SILYLDIAZOALKANEN Me3Si(LnM)CN2
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Silyldiazoalkanes Me3Si(LnM)CN2 (LnM = Me3Ge, Me3Sn, Me3Pb; Me2As, Me2Sb, Me2Bi) have been synthesized by three different routes: (a) reactions of Me3SiCHN2 with metal amides LnMNR1R2 of Group IVB and VB elements, using Me3SnCl as ca
- Glozbach, Eberhard,Lorberth, Joerg
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- Batch and Continuous-Flow One-Pot Processes using Amine Diazotization to Produce Silylated Diazo Reagents
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A novel synthesis of trimethylsilyldiazomethane (TMSCHN2) by diazotization of trimethylsilylmethylamine (TMSCH2NH2) is reported using batch and continuous flow synthesis. The latter affords a daily production of 275 g (2.4 mol) of TMSCHN2. Other silylated methylamines were also successfully reacted under the developed reaction conditions to furnish various silicon-bearing diazomethane reagents. The applicability of the process is highlighted by disclosure of batch and continuous flow one-pot esterification and 1,3-dipolar cycloaddition processes. Furthermore, the high-yielding esterification of carboxylic acids with silylated and substituted methylamines in continuous flow is disclosed. Finally, work-up and purification procedures are reported for the preparation of a 2-MeTHF solution of TMSCHN2, which can be used in rhodium-catalyzed methylenation and homologation reactions.
- Audubert, Clément,Gamboa Marin, Oscar Javier,Lebel, Hélène
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supporting information
p. 6294 - 6297
(2017/05/19)
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- Catalytic trimerization of bis-silylated diazomethane
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(Me3Si)2CNN isomerizes upon addition of traces of [Me3Si]+ ions to give (Me3Si)2NNC, which then undergoes an unusual trimerization reaction to give exclusively 4-diazenyl-3-hydrazinylpyrazo
- Ibad, Muhammad Farooq,Langer, Peter,Rei?, Fabian,Schulz, Axel,Villinger, Alexander
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supporting information
p. 17757 - 17768
(2013/01/15)
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- Rhodium-catalyzed synthesis of terminal alkenes
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Terminal alkenes have been efficiently prepared via a rhodium-catalyzed olefination procedure using Wilkinson's catalyst in the presence of triphenylphosphine, 2-propanol and trimethylsilyldiazomethane. Optimized reaction conditions are described for aldehydes and ketones, as well as alternative work up procedures. Georg Thieme Verlag Stuttgart.
- Paquet, Valerie,Lebel, Helene
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p. 1901 - 1905
(2007/10/03)
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- Trimethylsilyldiazomethane - A mild and efficient reagent for the methylation of carboxylic acids and alcohols in natural products
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Esterification of various naturally occurring carboxylic acids with trimethylsilyldiazo-methane proceeds nearly quantitatively under very mild conditions. Furthermore, highly sterically hindered alcohols can be converted directly to the corresponding methyl ethers. Improved methods for the preparation and quantification of this reagent are described. Springer-Verlag 2004.
- Presser, Armin,Huefner, Antje
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p. 1015 - 1022
(2007/10/03)
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- Rearrangement Approaches to Cyclic Skeletons. IV. The Total Synthesis of (+/-)-Pinguisone and (+/-)-Deoxopinguisone Based on Photochemical Acyl Migration of a Bicyclonon-6-en-2-one
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The total synthesis of (+/-)-Pinguisone (2) and (/-)-deoxopinguisone (3), fused ring sesquiterpenes, has been achieved starting from 1-methoxy-3,4,5-trimethylbenzene. 1-Methoxy-4,5,endo-8-trimethylbicyclonon-5-en-2-one (9) was prepared selectively via facial selective Diels-Alder reaction of the diene derived from the benzene and 2-chloroacrylonitrile.Ring enlargement of 9 using (CH3)3SiCHN2 and BF3 etherate gave the corresponding bicyclooct-en-2-one (8).The photochemical acyl migration of 8 gave the fused-ring compound (7).The fourth methyl was introduced selectively by the conjugate addition of (CH3)2CuLi to the spironon-8-ene-3,2'-dioxolan>-7-one prepared from 7.Each furan ring of 2 and 3 was constructed via the corresponding butenolide derived from the γ-keto acid by acid-catalyzed dehydration.
- Uyehara, Tadao,Kabasawa, Yasuhiro,Kato, Tadahiro
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p. 2521 - 2528
(2007/10/02)
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- Process for preparing trialkylsilyldiazomethanes
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A process for preparing trialkylsilyldiazomethanes in which halomethyltrialkylsilane represented by the general formula R1 R2 R3 SiCH2 X (wherein R1, R2 and R3 denote an alkyl gr
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- A CONVENIENT, HIGH YIELD SYNTHESIS OF TRIMETHYLSILYLDIAZOMETHANE
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A new one step synthesis of trimethylsilyldiazomethane is described.
- Martin, Michael
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p. 809 - 812
(2007/10/02)
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- New Methods and Reagents in Organic Synthesis. 28. A Convenient and Efficient Preparation of Trimethylsilyldiazomethane (TMSCHN2) using Diphenyl Phosphoroazidate (DPPA)
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The stable and safe compound trimethylsilyldiazomethane (TMSCHN2), which is useful for organic synthesis, was prepared in high yield by diazo-transfer reaction of trimethylsilylmethylmagnesium chloride with diphenyl phosphoroazidate
- Mori, Shigehiro,Sakai, Izumi,Aoyama, Toyohiko,Shioiri, Takayuki
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p. 3380 - 3382
(2007/10/02)
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