A Photochemical Approach to a Potential Precursor of the Bicyclo [6.4.0] Dodecane Ring System of Taxane Diterpenes

The intermolecular [2+2] photocycloaddition of dimedone 6 and 1-acetoxy-2-methyl-5-dioxolan-1-hexene 7 followed by alkaline treatment, gave the 1,5,5,11-tetramethyl-7-dioxolan bicyclo [4,3,2]-4-decen-2,3-dione 12, and the 1,5,5-trimethyl-3-hydroxy-7-dioxolan bicyclo [5,4,1] dodecan-2,11-dione 13.     

A New Synthetic Approach to Functionalized Bicyclo[3.2.1]octanes

Russian Journal of General Chemistry - The reaction of furfural with secondary amines and isopropyl cyanoacetate gave previously unkown diisopropyl esters of...     

Theoretical Study of the Photochemical Reaction Mechanism of Bicyclo [4.1.0 ] heptane

IntroductionPhotochemical reactions, which involve a three-membered ring, have been of great interest to experi-mental photochemists[1—10]. A main reason for thisphenomenon is that the cyclopropane ring exhibits somereaction characteristics of double bon…     

A Remarkable Synthesis of the Bicyclo[4.2.1]Nonenedione System

Allylation of the C-2 enolate of the bicyclo[3.3.1]nonenedione 1 proceeds with an unusual acyl migration to yield the C-allyl ester 5 of the rearranged bicyclo[4.2.1]nonenedione system.     

Bicyclo[5.3.1]undec-1(10)-ene bridgehead olefin stability and the taxane bridgehead olefin

MM2 calculations have shown how substituent and conformational effects play a role in the stabilities of systems containing the bicyclo[5.3.1]undec-I(10)-ene moiety and that the taxane diterpene skeleton which possesses this structural feature is surprisingly stable.     

Photochemical Rearrangements of Chiral Bicyclo[2.2.2]oct-5-en-2-Ones1

Photochemical oxadi-π-methane rearrangement (1,2-acyl shift) of the chiral bicyclo[2.2.2]oct-5-en-2-ones 2 and 3 furnishes the tricyclic ketones 5 and 6 , whereas the 1,3-acyl shift generates the cyclobutanones 7 and 8 respectively.     

Sodium Bicyclo[1.1.1]pentanesulfinate: A Bench-Stable Precursor for Bicyclo[1.1.1]pentylsulfones and Bicyclo- [1.1.1]pentanesulfonamides

Herein, we present the synthesis of the bench-stable sodium bicyclo[1.1.1]pentanesulfinate (BCP-SO₂Na) and its application in the synthesis of bicyclo[1.1.1]pentyl (BCP) sulfones and sulfonamides. The salt can be obtained in a four-step procedure from commercially available precursors in multigram scale without the need for column chromatography or crystallization. Sulfinates are known to be useful precursors in radical and nucleophilic reactions and are widely used in medicinal chemistry. This building block enables access to BCP sulfones and sulfonamides avoiding the volatile [1.1.1]propellane which is favorable for the extension of SAR studies. Further, BCP-SO₂Na enables the synthesis of products that were not available with previous methods. A chlorination of BCP-SO₂Na and subsequent reaction with a Grignard reagent provides a new route to BCP sulfoxides. Several products were analyzed by single-crystal X-ray diffraction.     

Photochemical Studies on Bicyclo[2.1.1]hexyl Derivatives: Chemical Behavior and Asymmetric Induction

The photochemical behavior of bicyclo[2.1.1]hexyl derivatives was investigated by irradiation with a 450 W medium‐pressure mercury lamp in acetonitrile solution. The irradiation of methyl bicyclo[2.1.1]hexane‐5‐carbonylbenzoate ( 1a ) led to both Norrish type II cyclization and cleavage products with a molar ratio of 1:2.2, whereas the irradiation of methyl 5‐methylbicyclo[2.1.1]hexane‐5‐carbonylbenzoate ( 1b ) afforded the only Norrish/Yang photocyclization compound as the sole product. Such results were illustrated by several geometric parameters for Norrish/Yang photoreaction as ?₁, ?₄ and β obtained from the crystal structures. Furthermore, asymmetric photochemical studies using ionic chiral auxiliary technique were also conducted in the solid state.     

An Efficient Approach to the [1,2,4]-Triazolo[3,2-d][1,5]Benzoxazepine Skeleton-A Novel Tricyclic Ring System

Unprecedented [1,2,4]-Triazolo[3,2-d][1,5]benzoxazepine skeleton was easily achieved by cycloaddition of the allene-like cations 3, derived from 4-chromanone arylhydrazones, to the triple bond of nitriles and ensuing ring enlargement. The structural assignment of one product (5d) has been ultimately accomplished by X-ray diffraction analysis.     

Photochemical Approach to the Cyclohepta[b]indole Scaffold by Annulative Two-Carbon Ring-Expansion

We report on the implementation of the concept of a photochemically elicited two-carbon homologation of a π-donor–π-acceptor substituted chromophore by triple-bond insertion. Implementing a phenyl connector between the slide-in module and the chromophore enabled the synthesis of cylohepta[b]indole-type building blocks by a metal-free annulative one-pot two-carbon ring expansion of the five-membered chromophore. Post-irradiative structural elaboration provided founding members of the indolo[2,3-d]tropone family of compounds. Control experiments in combination with computational chemistry on this multibond reorganization process founded the basis for a mechanistic hypothesis.