ABSTRACT
Dehydroepiandrosterone (3ß-hydroxyandrost-5-en-17-one) (DHEA) is a naturally occurring steroid hormone primarily produced in the zona reticularis of the human adrenal glands. It serves as a crucial precursor for sex hormones, such as testosterone, estradiol, and androstenedione. Recent findings indicate that DHEA serves as the primary source of sex steroids in women during both pre- and postmenopausal stages. Additionally, a decline in DHEA levels with age is linked to various hormone-deficiency symptoms. Despite the wide array of biological activities that make DHEA a valuable polycyclic natural steroid, particularly for pharmaceutical and cosmetic applications, reports suggest that oral DHEA has limited clinical effect. Thus, A- and D-ring modified DHEA are synthesized and their biological activities are carried out by different research groups and enhanced biological activity reported in the literature. Here, in this review, we have tried to cover all of the synthetic routes and biological studies of modified A- and D-ring DHEA from 2015 to mid-2022.
ABSTRACT
A phosphite-mediated [2,3]-aza-Wittig rearrangement has been developed for the regio- and enantioselective allylic alkylation of six-membered heteroaromatic compounds (azaarenes). The nucleophilic phosphite adducts of N-allyl salts undergo a stereoselective base-mediated aza-Wittig rearrangement and dissociation of the chiral phosphite for overall C-H functionalization of azaarenes. This method provides efficient access to tertiary and quaternary chiral centers in isoquinoline, quinoline, and pyridine systems, tolerating a broad variety of substituents on both the allyl part and azaarenes. Catalysis with chiral phosphites is also demonstrated with synthetically useful yields and enantioselectivities.
ABSTRACT
A catalyst bound α-aminoalkyl radical intermediate from iminium is developed to control its formation and reactivity with aerobic oxygen. The influence of the catalyst was demonstrated via the ease of radical intermediate formation and its subsequent reactivity, including the first catalyst-controlled enantioselective aerobic oxidation with a chiral phosphite catalyst.