Synthesis of Deoxyaspidodispermine Based on a Functional Protecting Group Strategy

Abstract

A synthesis of deoxyaspidodispermine was produced from homotyramine. This approach is based on the application of a functional protecting group strategy that not only masks the reactivity of sensitive groups during crucial steps but also possesses a moiety desired in the final target, which is transferred to the substrate at the time of deprotection. This synthesis highlights an aza-Michael–Smiles ring-closure cascade, which enables the formation of a tetracyclic system from a nosylamide protecting group.

Towards routine organic structure determination using Raman microscopy

“…With this goal in mind, we followed a recently reported total synthesis of deoxyaspidodispermine using Raman microscopy as a structure elucidation tool. 9 A total of 6 structures, molecules 16 to 21 ( Fig. 8A ), were isolated and analyzed by Raman microscopy (see ESI † for experimental and theoretical spectra).…”

“…We demonstrate DFT-correlated spectral matching in several proof-of-concept examples, including the match of synthetic intermediates from the total synthesis of deoxyaspidodispermine. 9 Method SARA, or "Similarity Assessment of Raman Arrays", is the name given to the soware written by author J. M. to process Raman spectra. It was programmed in numerical Python with a certain level of automation in mind and runs in seconds.…”

“…We demonstrate DFT-correlated spectral matching in several proof-of-concept examples, including the match of synthetic intermediates from the total synthesis of deoxyaspidodispermine. 9 …”

Synthesis of 2‐Amino‐3‐arylindoles and their Fused Analogues via Intramolecular C‐Arylation

“…In addition, we applied the intermediate 4 w to the formation of 7,8-dihydrobenzo [6,7][1,3]diazepino [4,5b]indole scaffold. The product 10 a was easily synthesized in two steps via catalytic hydrogenation followed by triethyl orthoformate-mediated cycliza tion (Scheme 8).…”

“…Recently, the Truce-Smiles rearrangement of natural amino acid-based 2/4nitrobenzenesulfonamides was widely investigated as a route to different nitrogen heterocycles via Cαarylation, in which CÀ H was typically activated by the adjacent carbonyl group (Scheme 1). [3][4][5][6][7][8] Inspired by this approach, we suggested the use of 2/4-nitrobenzenesulfonamides originating from 2-aminobenzyl cyanide alkylated by scaffolds without electron-withdrawing groups. Consequently, instead of undergoing Cα-arylation, these substrates may be amenable to Cγ-Scheme 1.…”