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The implementation of a web-based stereochemistry tutorial, which allows students to select their preferred structural representation and method for making stereochemical comparisons between molecules, is discussed. The tutorial was evaluated by students in three different introductory organic chemistry courses at a large midwestern university. The data show that students did use a variety of different methods for making stereochemical comparisons between molecules and that prior exposure to lectures on stereochemistry by the course professor strongly influenced these choices. Furthermore, the level of improvement in stereochemical knowledge as a result of using only the tutorial was comparable to, or higher than, that achieved by students who were only exposed to lectures by the course professor, regardless of the method chosen for making stereochemical comparisons between molecules.

A Web-based stereochemistry tutorial is described that details the core definitions and structural representations of stereochemistry in an organic chemistry course. The Cahn–Ingold–Prelog rules and their application for assigning R and S orientations to stereocenters and E and Z orientations to alkenes are discussed. This tutorial is unique in allowing students to determine their preferred structural representation of organic molecules and select their own method for making stereochemical comparisons between these molecules. The remaining content of the comparison section of the tutorial is presented using the method that the student selected.

Photolysis (λ472 nm) of 2-diazo-3-pentyne (11) affords triplet 1,3-dimethylpropynylidene (MeC3Me, (3)3), which was characterized spectroscopically in cryogenic matrices. The infrared, electronic absorption, and electron paramagnetic resonance spectra of MeC3Me ((3)3) are compared with those of the parent system (HC3H) to ascertain the effect of alkyl substituents on delocalized carbon chains of this type. Quantum chemical calculations (CCSD(T)/ANO1) predict an unsymmetrical equilibrium structure for triplet MeC3Me ((3)3), but they also reveal a very shallow potential energy surface. The experimental IR spectrum of triplet MeC3Me ((3)3) is best interpreted in terms of a quasilinear, axially symmetric structure. EPR spectra yield zero-field splitting parameters that are typical for triplet carbenes with axial symmetry (|D/hc| = 0.63 cm(-1), |E/hc| = ∼ 0 cm(-1)), while theoretical analysis suggests that the methyl substituents confer significant spin polarization to the carbon chain. Upon irradiation into the near-UV electronic absorption (λmax 350 nm), MeC3Me ((3)3) undergoes 1,2-hydrogen migration to yield pent-1-en-3-yne (4), a photochemical reaction that is typical of carbenes bearing a methyl substituent. This facile process apparently precludes photoisomerization to other interesting C5H6 isomers, in contrast to the rich photochemistry of the parent C3H2 system.

A variety of substituted pentadiynols, -diynals, and -diynones have been prepared en route to precursors to dialkynyl carbenes (R(1)-C≡C-C-C≡C-R(2)). In light of the marginal stability associated with these simple systems, several strategies were required to assemble the carbon backbones. The requisite five-carbon skeletons were prepared using 4 + 1, 3 + 2, 2 + 2 + 1, and 2 + 1 + 1 + 1 coupling methodologies. The Dess-Martin periodinane serves as an excellent method for the oxidation of pentadiynols to diynals and diynones, although many of the oxidized products are sufficiently reactive that they were not isolated; rather, they were generated in situ and intercepted with nucleophiles such as tosylhydrazide or trisylhydrazide. The hydrazone derivatives are generally reliable precursors to diazo compounds and carbenes, although cyclization of the hydrazone to afford a pyrazole can be a complicating factor in certain instances.

Triplet carbenes t-butylpentadiynylidene (t-BuC(5)H, 1a) and dimethylpentadiynylidene (MeC(5)Me, 1b) have been produced photochemically from their corresponding diazo compound precursors and studied spectroscopically in cryogenic matrices (N(2) or Ar) at 10 K. The infrared, electronic absorption, and electron paramagnetic resonance spectra of these species exhibit numerous similarities to the spectra of pentadiynylidene (HC(5)H) and methylpentadiynylidene (MeC(5)H) recorded previously. EPR spectra yield zero-field splitting parameters that are typical for triplet carbenes with axial symmetry (t-BuC(5)H, 1a: |D/hc| = 0.61 cm(-1), |E/hc| ∼ 0 cm(-1); MeC(5)Me, 1b: |D/hc| = 0.62 cm(-1), |E/hc| ∼ 0 cm(-1)). Electronic spectra are characterized by weak absorptions (T(1) ← T(0)) in the near-UV and visible region (350-430 nm) with extended vibronic progressions. The electronic transitions of several -C(5)- carbenes are compared, and an apparent dependence of the transition wavelength on the level of alkyl substitution of the carbon chain is found. Chemical trapping of triplet 1a in an O(2)-doped matrix affords carbonyl oxides derived predominantly from attack at C-3. Both t-BuC(5)H (1a) and MeC(5)Me (1b) undergo photochemical rearrangement upon UV irradiation.