Synthesis of Ajoene Analogues by Novel Synthetic Strategies.

Ajoene is a compound found in garlic extracts exhibiting a large range of biological activity. Novel ajoene analogues have been prepared in the search of compounds with superior bioactivity. Modifications include the alteration of the sulfoxide, the central alkene and the terminal allyl groups.

Short Total Synthesis of Ajoene, (E,Z)-4,5,9-Trithiadodeca-1,6,11-triene 9-oxide, in Batch and (E,Z)-4,5,9-Trithiadodeca-1,7,11-triene in Continuous Flow.

A short total synthesis of ajoene, (E,Z)-4,5,9-trithiadodeca-1,6,11-triene 9-oxide, has been achieved over six steps. In addition, a continuous flow synthesis under mild reaction conditions to (E,Z)-4,5,9-trithiadodeca-1,7,11-triene is described starting from simple and easily accessible starting materials. Over four steps including propargylation, radical addition of thioacetate, deprotection, and disulfide formation/ allylation, the target product can be obtained at a rate of 0.26 g h-1 in an overall yield of 12 %.

Short Total Synthesis of Ajoene.

We describe a short total synthesis of ajoene, a major biologically active constituent of garlic. The instability of allicin as the only other known alternative starting material has led to the development of a reliable procedure for the synthesis of ajoene from simple building blocks that is also suitable for upscale operations.

Applications of enantioselective carbolithiation of ortho-substituted beta-methylstyrenes.

The enantioselective carbolithiation of ortho-substituted (E)-beta-methylstyrenes provides access to chiral lithiated intermediates with broad synthetic potential. Specifically, beta-methylstyrenes with o-aminomethyl, ether, and oxazoline groups have been employed in the synthesis of chiral aromatics and heteroaromatics such as isoquinolines, isoquinolinones, benzofurans, and isobenzofuranones.