Chemists have long envied the ability of enzymes to manipulate reaction energetics and specificity through steric confinement and precise functional-group interactions. The enormous rate accelerations that enzymes achieve at modest temperatures may be attributed to their high degree of complexity, and the synthetic chemist is hard pressed to create such well-constructed catalytic scaffolds. Yet...

The catalytic asymmetric aminoallylation of chiral aldehydes is developed as a new method for the catalyst controlled synthesis of syn- and anti-1,3-aminoalcohols. This methodology is highlighted in the synthesis of the sedum alkaloids (+)-sedridine and (+)-allosedridine both of which have their final carbon incorporated during closure of the piperidine ring via a hydroformylation with formalde...

Heterologous expressions and purifications of all WelU proteins from the welwitindolinone pathways in Hapalosiphon welwitschii UTEX B1830 and IC-52-3 led to the discovery that WelU1 and WelU3 selectively assemble 12-epi-fischerindole U (2) and 12-epi-hapalindole C (1), respectively, from 3-geranyl 3-isocyanovinyl indolenine (4) via an enzymatic cascade featuring the Cope rearrangement, stereose...

Benign prostatic hyperplasia (BPH) is a non-malignant enlargement of the prostate gland. Itis a leading disorder of the elderly male population. Excessive production of dihydrotestosteronehas been implicated in this pathological condition. Steroidal 5α-reductase is a membrane boundNADPH dependent enzyme which is responsible for the conversion of testosterone (T) todihydrotestosterone (DHT). The...

Key words (±)-talatisamine - Diels–Alder reaction [2+2] photo-cycloaddition Lemieux–Johnson oxidation retro-aldol–aldol Wagner–Meerwein rearrangement aza-Prins

A study of microwave-induced and standard thermal Overman rearrangement of selected allylic trichloroacetimidates 1a-1f, 6-8 to the corresponding acetamides 2a-2f, 9-11 is reported. The microwave-assisted rearrangement of trifluoroacetimidate 13 is also described. Using this methodology, an efficient access to versatile allylic trihaloacetamides building synthons was established.