40359-32-8Relevant articles and documents
Synthesis of treprostinil: Key claisen rearrangement and catalytic pauson-khand reactions in continuous flow
García-Lacuna, Jorge,Domínguez, Gema,Blanco-Urgoiti, Jaime,Pérez-Castells, Javier
, p. 9489 - 9501 (2019)
A new synthesis of treprostinil is described using a plug flow reactor in two of the key steps. First, a Claisen rearrangement reaction is described in scaled flow at multigram amounts. Yields and selectivity of this step are sharply improved compared to those from previous syntheses. Second, the key Pauson-Khand reaction in flow is described under catalytic conditions with 5 mol% of cobalt carbonyl and only 3 equiv. of CO. Scaling up of this reaction safely ensures a good yield of an advanced intermediate which is transformed into treprostinil in three steps. Other improvements are the introduction of the carboxymethyl chain into the phenol from the beginning to reduce the protection-deprotection steps. The synthesis is completed in 14% global yield after 12 linear steps from (S)-epichlorhydrin.
Turn on chemiluminescence-based probes for monitoring tyrosinase activity in conjunction with biological thiols
Shelef, Omri,Sedgwick, Adam C.,Pozzi, Sabina,Green, Ori,Satchi-Fainaro, Ronit,Shabat, Doron,Sessler, Jonathan L.
supporting information, p. 11386 - 11389 (2021/11/09)
We report a chemiluminescent probe (CLPT1) that permits the paired detection of tyrosinase (Tyr) and biological thiols. Tyr only leads to a poor chemiluminescence response, a finding ascribed to the formation of a stableo-benzoquinone intermediate. The addition of glutathione (GSH), or ascorbate to theo-benzoquinone intermediate results in thiol conjugation or reduction to this intermediate, respectively. This produces a strong chemiluminescence response. Thiol co-dependence was demonstrated in live cells using the cell permeable analogue,CLPT3. The present chemiluminescence-based strategy allows the concurrent detection of tyrosinase activity and biological thiols.
Visible-light mediated facile dithiane deprotection under metal free conditions
Dharpure, Pankaj D.,Bhowmick, Anindita,Warghude, Prakash K.,Bhat, Ramakrishna G.
, (2019/12/09)
Visible light mediated facile and selective dithiane deprotection under metal free conditions is developed. Eosin Y (1 mol%) proved to be an effective catalyst for the dithiane deprotection under the ambient photoredox conditions. The standard household compact fluorescent light source (CFL bulb) proved to be effective under open-air conditions in aqueous acetonitrile at room temperature. The protocol that exhibits a broad substrate scope and functional group tolerance has been shown to expand to a range of transformations for the electron-rich and -deficient thioacetals and thioketals. The synthetic utility of this protocol has also been demonstrated by gram-scale application.