1,023 research outputs found
Aryne Acyl-Alkylation in the General and Convergent Synthesis of Benzannulated Macrolactone Natural Products: An Enantioselective Synthesis of (−)-Curvularin
A general approach for the synthesis of benzannulated macrolactone natural products utilizing an aryne acyl-alkylation reaction is described. Toward this end, the total syntheses of the natural products (−)-curvularin, curvulin, and (−)-diplodialide C are reported. Furthermore, the aryne insertion technology has enabled the rapid conversion of simple diplodialide natural products to curvularin, thereby connecting these two biosynthetically distinct classes of compounds via synthetic methods
A Comparison of Ability Grouping and Individualized Reading for Slow Learners Taught Under Regular Classroom Conditions
Palladium-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to Five-, Six-, and Seven-Membered β-Substituted Cyclic Enones: Enantioselective Construction of All-Carbon Quaternary Stereocenters
The first enantioselective Pd-catalyzed construction of all-carbon quaternary stereocenters via 1,4-addition of arylboronic acids to β-substituted cyclic enones is reported. Reaction of a wide range of arylboronic acids and cyclic enones using a catalyst prepared from Pd(OCOCF_3)_2 and a chiral pyridinooxazoline ligand yields enantioenriched products bearing benzylic stereocenters. Notably, this transformation is tolerant to air and moisture, providing a practical and operationally simple method of synthesizing enantioenriched all-carbon quaternary stereocenters
Permutation-invariant distance between atomic configurations
We present a permutation-invariant distance between atomic configurations,
defined through a functional representation of atomic positions. This distance
enables to directly compare different atomic environments with an arbitrary
number of particles, without going through a space of reduced dimensionality
(i.e. fingerprints) as an intermediate step. Moreover, this distance is
naturally invariant through permutations of atoms, avoiding the time consuming
associated minimization required by other common criteria (like the Root Mean
Square Distance). Finally, the invariance through global rotations is accounted
for by a minimization procedure in the space of rotations solved by Monte Carlo
simulated annealing. A formal framework is also introduced, showing that the
distance we propose verifies the property of a metric on the space of atomic
configurations. Two examples of applications are proposed. The first one
consists in evaluating faithfulness of some fingerprints (or descriptors), i.e.
their capacity to represent the structural information of a configuration. The
second application concerns structural analysis, where our distance proves to
be efficient in discriminating different local structures and even classifying
their degree of similarity
The Enantioselective Tsuji Allylation
The first catalytic enantioselective examples of the Tsuji allylation using enol carbonates and enol silanes are described. The products possess a quaternary stereogenic center and are useful building blocks for synthetic chemistry
Enantioselective construction of the tricyclic core of curcusones A–D via a cross-electrophile coupling approach
Herein we report our recent progress toward the enantioselective total synthesis of the diterpenoid natural products curcusones A–D by means of complementary Stetter annulation or ring-closing metathesis (RCM) disconnections. Using the latter approach, we have achieved the concise construction of the 5–7–6 carbocyclic core embedded in each member of the curcusone family. Essential to this route is the use of a cross-electrophile coupling strategy, which has not previously been harnessed in the context of natural product synthesis
Regioselective Reactions of Highly Substituted Arynes
The fully regioselective reactivity of four new highly substituted silyl aryl triflate aryne precursors in aryne acyl-alkylation, acyl-alkylation/condensation, and heteroannulation reactions is reported. The application of these more complex arynes provides access to diverse natural product scaffolds and obviates late-stage functionalization of aromatic rings
Pd-catalyzed enantioselective aerobic oxidation of secondary alcohols: Applications to the total synthesis of alkaloids
Enantioselective syntheses of the alkaloids (-)-aurantioclavine, (+)-amurensinine, (-)-lobeline, and (-)- and (+)-sedamine are described. The syntheses demonstrate the effectiveness of the Pd-catalyzed asymmetric oxidation of secondary alcohols in diverse contexts and the ability of this methodology to set the absolute configuration of multiple stereocenters in a single operation. The utility of an aryne C-C insertion reaction in accessing complex polycyclic frameworks is also described
Mechanistic analysis of an asymmetric palladium-catalyzed conjugate addition of arylboronic acids to β-substituted cyclic enones.
An asymmetric palladium-catalyzed conjugate addition reaction of arylboronic acids to enone substrates was investigated mechanistically. Desorption electrospray ionization coupled to mass spectrometry was used to identify intermediates of the catalytic cycle and delineate differences in substrate reactivity. Our findings provide evidence for the catalytic cycle proceeding through formation of an arylpalladium(II) cation, subsequent formation of an arylpalladium-enone complex, and, ultimately, formation of the new C-C bond. Reaction monitoring in both positive and negative ion modes revealed that 4-iodophenylboronic acid formed a relatively stable trimeric species under the reaction conditions
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