Synthetic Doping of Diamondoids through Skeletal Editing

Abstract

We present a strategy for the skeletal editing of diamondoid structures to selectively displace methylene for heteroatom moieties in the carbon framework. This constitutes a synthetic approach to doping diamond-like structures with electron donor dopants (O, N, and S). The key steps involve two subsequent retro-Barbier fragmentations followed by cage reconstruction in the presence of a dopant. Remarkably, the incorporation of n-dopants reduces the strain of the diamondoid cage as shown through homodesmotic equations.

Recent ring distortion reactions for diversifying complex natural products

“…The above successful examples illustrate the application of new synthetic methodologies in distortion of NPs rings can facilitate synthesis of natural product-like molecules. Recently developed synthetic methodologies, for example, photochemical catalytic reactions, 84 electrochemical synthesis 85,86 and skeletal editing 87,88 are expected to have great impact on ring distortion reactions.…”

Heat Capacity Estimation Using a Complete Set of Homodesmotic Reactions for Organic Compounds

“…Thus, in the 21st century, more than 500 scientific materials have been published that use the concept of homodesmoticity to obtain various types of thermochemical information. It may provide few illustrative examples of recent publications using the homodesmotic method for calculating the enthalpy characteristics of organic molecules and radicals [8][9][10][11][12][13][14][15][16], quantitative description of aromaticity [17][18][19], determination of strain energies in cyclic structures and compounds of a complex structure [20][21][22][23][24][25][26][27]. As with additive approaches, the homodesmotic method Molecules 2022, 27, 7814 2 of 15 is convenient for the algorithmization and application of computational technologies in thermochemical analysis [28][29][30][31][32][33].…”

Borylated Cyclopropanes as Spring-Loaded Entities: Access to Vicinal Tertiary and Quaternary Carbon Stereocenters in Acyclic Systems

“…Even though various strategies have appeared over the years, protocols for the selective formation of vicinal stereocenters of either tertiary or quaternary nature are still rather limited . In this context, the carbon–carbon bond cleavage of densely functionalized cyclopropanes as a new approach of molecular editing has gained increased momentum over the past few years, as it provides an innovative solution for the creation of well-defined stereocenters along acyclic hydrocarbon architectures from an easily accessible cyclopropyl platform . We have recently reported a nucleophilic substitution reaction at the quaternary carbon center of cyclopropyl carbinol derivatives, with a pure inversion of configuration, to access tertiary alkyl halides and esters as a single diastereomer (Scheme , top) .…”