Phenylselenoethers as Precursors of Acyclic Free Radicals. Creating Tertiary and Quaternary Centers Using Free Radical-Based Intermediates

Stereoselective Quaternary Center Construction via Atom-Transfer Radical Cyclization Using Silicon Tethers on Acyclic Precursors

“…In the past decade, we have explored the reactivity of carbon-centered free radicals on acyclic molecules in various transformations including carbon−carbon bond-forming reactions, as illustrated in Scheme . We have demonstrated that diastereoselectivity and high yields could be achieved in many of these reactions provided that certain conditions are present …”

Stereopentads Derived from a Sequence of Mukaiyama Aldolization and Free Radical Reduction on α-Methyl-β-alkoxy Aldehydes: A General Strategy for Efficient Polypropionate Synthesis

“…Obviously, the introduction of a protecting group on the oxygen at C(3) could achieve such goal with the downside of adding steps to our process. We have discovered that Bu 2 BOTf was an optimal solution to this problem. , Indeed, this Lewis acid reacts with the hydroxyl at C(3) to generate the dialkyl borinate in situ in the presence of a base, such as DIEA. The resulting product does not need to be isolated prior to the hydrogen transfer reaction, and the borinate can be released easily in the subsequent workup of the reaction.…”

“…Our group designed a conceptually different strategy in which no mismatched scenarios should be observed . Central to our strategy is a substrate control approach involving the two reactions depicted in Figure .…”

Stereocontrolled Synthesis of C1−C17 Fragment of Narasin via a Free Radical-Based Approach

“…The 2,3- anti isomer could be obtained by taking advantage of the acyclic stereoselection (T.S. I ) . A boron-based Lewis acid (Bu 2 BOTf) and DIEA were used in this case to create a borinate that serves as a temporary protecting group.…”