Towards routine organic structure determination using Raman microscopy.

Raman microscopy can reveal a compound-specific vibrational "fingerprint" from micrograms of material with no sample preparation. We expect this increasingly available instrumentation to routinely assist synthetic chemists in structure determination; however, interpreting the information-dense spectra can be challenging for unreported compounds. Appropriate theoretical calculations using the highly efficient rSCAN-3c method can accurately predict peak positions but are less precise in matching peak heights.

Copper-Photocatalyzed Hydroboration of Alkynes and Alkenes.

The photocatalytic hydroboration of alkenes and alkynes is reported. The use of newly-designed copper photocatalysts with B Pin permits the formation a boryl radical, which is used for hydroboration of a large panel of alkenes and alkynes. The hydroborated products were isolated in high yields, with excellent diastereoselectivities and a high functional group tolerance under mild conditions.

Metal-Free-Visible Light C-H Alkylation of Heteroaromatics via Hypervalent Iodine-Promoted Decarboxylation.

A metal-free photoredox C-H alkylation of heteroaromatics from readily available carboxylic acids using an organic photocatalyst and hypervalent iodine reagents under blue LED light is reported. The developed methodology tolerates a broad range of functional groups and can be applied to the late-stage functionalization of drugs and drug-like molecules. The reaction mechanism was investigated with control experiments and photophysical experiments as well as DFT calculations.

Visible-Light-Initiated Manganese Catalysis for C-H Alkylation of Heteroarenes: Applications and Mechanistic Studies.

A visible-light-driven Minisci protocol that employs an inexpensive earth-abundant metal catalyst, decacarbonyldimanganese Mn (CO) , to generate alkyl radicals from alkyl iodides has been developed. This Minisci protocol is compatible with a wide array of sensitive functional groups, including oxetanes, sugar moieties, azetidines, tert-butyl carbamates (Boc-group), cyclobutanes, and spirocycles. The robustness of this protocol is demonstrated on the late-stage functionalization of complex nitrogen-containing drugs.