291525-79-6Relevant articles and documents
"Close-to-Release": Spontaneous Bioorthogonal Uncaging Resulting from Ring-Closing Metathesis
Sabatino, Valerio,Rebelein, Johannes G.,Ward, Thomas R.
, p. 17048 - 17052 (2019/10/11)
Bioorthogonal uncaging reactions offer versatile tools in chemical biology. In recent years, reactions have been developed to proceed efficiently under physiological conditions. We present herein an uncaging reaction that results from ring-closing metathesis (RCM). A caged molecule, tethered to a diolefinic substrate, is released via spontaneous 1,4-elimination following RCM. Using this strategy, which we term "close-to-release", we show that drugs and fluorescent probes are uncaged with fast rates, including in the presence of mammalian cells or in the periplasm of Escherichia coli. We envision that this tool may find applications in chemical biology, bioengineering and medicine.
Ortho-TMS benzaldehyde: An effective linchpin for type II anion relay chemistry (ARC)
Smith III, Amos B.,Kim, Won-Suk,Wuest, William M.
supporting information; experimental part, p. 7082 - 7086 (2009/04/07)
(Chemical Equation Presented) ARC de triomphe: Ortho-TMS benzaldehyde permits efficient multicomponent union of a variety of nucleophiles and electrophiles, including the first example of a Pd-mediated ARC Type II process. A proof-of-concept synthetic sequence was designed and implemented for construction of a focused library of natural product-like compounds (see scheme). ARC: anion relay chemistry.
Cyclization-cycloaddition cascade of rhodium carbenoids using different carbonyl groups. Highlighting the position of interaction
Padwa, Albert,Zhang, Zhijia J.,Zhi, Lin
, p. 5223 - 5232 (2007/10/03)
A series of 3-diazoalkanediones, when treated with a catalytic quantity of a rhodium(II) carboxylate, were found to afford oxabicyclic dipolar cycloadducts derived by the trapping of a carbonyl ylide intermediate. The reaction involves generation of the 1,3-dipole by intramolecular cyclization of the keto carbenoid onto the oxygen atom of the neighboring keto group. Both five- and six-ring carbonyl ylides are formed with the same efficiency. A study of the tandem cyclization-cycloaddition cascade of several α-diazo ketoesters was also carried out, and the cascade sequence proceeded in high yield. When the interacting keto carbonyl group was replaced by an imido group, the rhodium(II)-catalyzed reaction proceeded uneventfully. In contrast, α-diazo amidoesters do not undergo nitrogen extrusion on treatment with a Rh(II) catalyst. Instead, the diazo portion of the molecule undergoes 1,3-dipolar cycloaddition with various dipolarophiles to give substituted pyrazoles as the final products.
Tandem Cyclization-Cycloaddition Reaction of Rhodium Carbenoids. Studies Dealing with Intramolecular Cycloadditions
Padwa, Albert,Hornbuckle, Susan F.,Fryxell, Glen E.,Zhang, Zhijia J.
, p. 5747 - 5757 (2007/10/02)
A series of 5-alkenyl-1-diazo-2,5-pentanediones, when treated with a catalytic quantity of rhodium(II) acetate, were found to give cycloadducts derived from the intramolecular trapping of a carbonyl ylide intermediate.Tethers of three or four methylenes r
