Untersuchungen an Diazoverbindungen und Aziden, LV. 7‐(Diazomethyl)cycloheptatriene durch elektrophile Diazoalkansubstitution

Abstract

Investigations on Diazo Compounds and Azides, LV1) 7-(Diazomethyl)cycloheptatrienes by Elertrophilic Diazoalkane SubstitutionThe silver-(diazomethy1)phosphoryl compounds 2a -c smoothly undergo electrophilic diazoalkane substitution with 1 to give 3a-c. In contrast, a more complex product formation is encountered in the reaction of 1 with the mercury-bis(diazomethylcarbony1) compounds 4a -d: Besides the 7-(diazomethyl)cycloheptatrienes 5 a -d the styrene derivatives 6a -c as well as the bromomercurio compounds 'la -d are formed. Probably the norcaradiene intermediates 12 and 14 play a role in the formation of 6 and 7. The reaction of the 7-(diazomethy1)cycloheptatrienes

How Nucleophilic Are Diazo Compounds?

“…Accordingly, in the reaction of phenyldiazomethane ( 1 b ) with (dma) 2 CH + OTf − , we observed a complex mixture of products, from which individual compounds could not be isolated. In agreement with Equation (1), Regitz and co‐workers observed that the reaction of tropylium bromide ( 19 ) with ethyl diazoacetate ( 1 e ) ( E + N =1.19) in the presence of triethylamine yielded ethyl (cycloheptatrienyl)diazoacetate ( 20 ) (Scheme ) 38. To achieve reactions with weaker electrophiles such as 2,4,6‐trialkylpyrylium ions, metallated diazo compounds have been employed 3…”

Modulating Escape Channels of Cycloheptatrienyl Rhodium Carbenes To Form Semibullvalene

“…We chose R to be a simple acetyl (Ac = COCH 3 ) group, given the body of the literature on acceptor and donor/acceptor carbenes . In addition, structures similar to (diazocarbonylmethyl)­cycloheptatriene ( A ) have been described in the literature …”

“…102 In addition, structures similar to (diazocarbonylmethyl)cycloheptatriene (A) have been described in the literature. 103 Exposure of A to a Rh catalyst (here, we model Rh 2 (OAc) 4 for simplicity) should lead to nitrogen extrusion to form Rhcarbene species C. The barrier for intramolecular CP of C to form Ac-SBV D (via TS C−D ) is predicted to be low (4.9 kcal mol −1 ). Formation of D is also predicted to be highly exergonic (−42.4 kcal mol −1 ), and its [3,3] rearrangement is predicted to require a 12.5 kcal mol −1 barrier (TS D−E ) to form the slightly less-favorable E (−38.6 kcal mol −1 ).…”

Silver Alkyls, Alkenyls, Aryls, and Alkynyls in Organic Synthesis

“…The thermally stable phosphoryl derivatives undergo electrophilic substitution with alkyl iodides 73 but, unlike the carbonyl-substituted derivatives, also undergo electrophilic diazoalkane substitution with a variety of H€ uckel aromatic salts (Scheme 1.31). [74][75][76][77][78][79] Disilver diazomethane has also been synthesized. When treated with an alkyne, it produces the corresponding silver acetylide.…”