Octahydrocyclopenta[c]pyridine Scaffold – Enantioselective Synthesis and Indole Annulation

An optically active hexahydrocyclopenta[c]pyridine derivative with quaternary stereocenter was prepared as a new heterocyclic scaffold. Key reaction was the Pd‐catalyzed asymmetric allylic alkylation of a piperidine‐based β‐oxoester, which proceeded in very good yield with high level of enantioselectivity (90 %, 95 % ee). The α‐allyl moiety was transformed into a 1,4‐diketone by Pd‐catalyzed Wacker oxidation with molecular oxygen (89 %). This intermediate was cyclized in an intramolecular aldol reaction furnishing the cyclopentenone motif (86 %). Hydrogenation of the C–C double bond gave the cis‐annulated octahydrocyclopenta[c]pyridine (86 %), which was submitted to Fischer indolization (85 %). Although two regioisomers could be expected, only the angular constitution was observed. Relative and absolute configurations were established by X‐ray crystallography of a para‐iodo benzamide derivative. The utility of the title compound as scaffold is further highlighted by a number of synthetically useful transformations, for instance formation of carboxamides, sulfonamides, ureas and reductive aminations with aldehydes

Octahydrocyclopenta[c]pyridine Scaffold – Enantioselective Synthesis and Indole Annulation

An optically active hexahydrocyclopenta[c]pyridine derivative with quaternary stereocenter was prepared as a new heterocyclic scaffold. Key reaction was the Pd‐catalyzed asymmetric allylic alkylation of a piperidine‐based β‐oxoester, which proceeded in very good yield with high level of enantioselectivity (90 %, 95 % ee). The α‐allyl moiety was transformed into a 1,4‐diketone by Pd‐catalyzed Wacker oxidation with molecular oxygen (89 %). This intermediate was cyclized in an intramolecular aldol reaction furnishing the cyclopentenone motif (86 %). Hydrogenation of the C–C double bond gave the cis‐annulated octahydrocyclopenta[c]pyridine (86 %), which was submitted to Fischer indolization (85 %). Although two regioisomers could be expected, only the angular constitution was observed. Relative and absolute configurations were established by X‐ray crystallography of a para‐iodo benzamide derivative. The utility of the title compound as scaffold is further highlighted by a number of synthetically useful transformations, for instance formation of carboxamides, sulfonamides, ureas and reductive aminations with aldehydes

Palladium-Catalyzed Construction of Quaternary Stereocenters by Enantioselective Arylation of γ-Lactams with Aryl Chlorides and Bromides

Herein, we report the first Pd‐catalyzed enantioselective arylation of α‐substituted γ‐lactams. Two sets of conditions were developed for this transformation, allowing for the use of either aryl chlorides or bromides as electrophiles. Utilizing a highly electron‐rich, dialkylphosphine ligand, we have been able to construct α‐quaternary centers in good yields (up to 91% yield) and high enantioselectivities (up to 97% ee)

Palladium-Catalyzed Construction of Quaternary Stereocenters by Enantioselective Arylation of γ-Lactams with Aryl Chlorides and Bromides

Herein, we report the first Pd‐catalyzed enantioselective arylation of α‐substituted γ‐lactams. Two sets of conditions were developed for this transformation, allowing for the use of either aryl chlorides or bromides as electrophiles. Utilizing a highly electron‐rich, dialkylphosphine ligand, we have been able to construct α‐quaternary centers in good yields (up to 91% yield) and high enantioselectivities (up to 97% ee)

Formation of δ‑Lactones by Cerium-Catalyzed, Baeyer–Villiger-Type Coupling of β‑Oxoesters, Enol Acetates, and Dioxygen

Formation of δ-lactones is observed when cyclopentanone-2-carboxylates are converted in a cerium-catalyzed reaction with α-aryl vinyl acetates under oxidative conditions. The products of this transformation possess a 1,4-dicarbonyl constitution together with a quaternary carbon center. Atmospheric oxygen is the oxidant in this process, which can be regarded as ideal from economic and ecological points of view. Further advantages of this new C–C coupling and oxidation reaction are its operational simplicity and the application of nontoxic and inexpensive CeCl₃·7 H₂O as precatalyst. This so far unprecedented reaction is proposed to proceed via 1,2-dioxane derivatives, which decompose under formation of an oxycarbenium cation in a Baeyer–Villiger-type pathway. This mechanistic picture is supported by the observation that electron-rich (donor substituted or heteroaromatic) enol esters give higher yields than electron deficient congeners. Apart from 1,4-diketones and α-hydroxylated β-oxoesters formed as byproducts, the yields of δ-lactones range from moderate to good (up to 74%)

Formation of δ‑Lactones by Cerium-Catalyzed, Baeyer–Villiger-Type Coupling of β‑Oxoesters, Enol Acetates, and Dioxygen

Formation of δ-lactones is observed when cyclopentanone-2-carboxylates are converted in a cerium-catalyzed reaction with α-aryl vinyl acetates under oxidative conditions. The products of this transformation possess a 1,4-dicarbonyl constitution together with a quaternary carbon center. Atmospheric oxygen is the oxidant in this process, which can be regarded as ideal from economic and ecological points of view. Further advantages of this new C–C coupling and oxidation reaction are its operational simplicity and the application of nontoxic and inexpensive CeCl₃·7 H₂O as precatalyst. This so far unprecedented reaction is proposed to proceed via 1,2-dioxane derivatives, which decompose under formation of an oxycarbenium cation in a Baeyer–Villiger-type pathway. This mechanistic picture is supported by the observation that electron-rich (donor substituted or heteroaromatic) enol esters give higher yields than electron deficient congeners. Apart from 1,4-diketones and α-hydroxylated β-oxoesters formed as byproducts, the yields of δ-lactones range from moderate to good (up to 74%)

Three-Component Reaction toward Polyannulated Quinazolinones, Benzoxazinones, and Benzothiazinones

An efficient conversion of readily accessible cyclic imines with acid chlorides, that are able to take part in nucleophilic aromatic substitution (S_NAr) reactions is realized in a new three-component, one-pot reaction, giving at least tricyclic annulated quinazolinones, benzoxazinones, and benzothiazinones as a result of the employed nitrogen, oxygen, or sulfur nucleophiles, respectively. Especially in the case of quinazolinones, this convenient strategy enables the access to heterocycles of heightened diversity, which offer the development of efficient derivatizations of the elaborated heterocyclic scaffolds. In a subsequent Heck or Ullmann cyclization, further annulations to the mentioned quinazolinones can be carried out

Three-Component Reaction toward Polyannulated Quinazolinones, Benzoxazinones, and Benzothiazinones

An efficient conversion of readily accessible cyclic imines with acid chlorides, that are able to take part in nucleophilic aromatic substitution (S_NAr) reactions is realized in a new three-component, one-pot reaction, giving at least tricyclic annulated quinazolinones, benzoxazinones, and benzothiazinones as a result of the employed nitrogen, oxygen, or sulfur nucleophiles, respectively. Especially in the case of quinazolinones, this convenient strategy enables the access to heterocycles of heightened diversity, which offer the development of efficient derivatizations of the elaborated heterocyclic scaffolds. In a subsequent Heck or Ullmann cyclization, further annulations to the mentioned quinazolinones can be carried out

Coulomb excitation of 31Mg

The ground state properties of 31Mg indicate a change of nuclear shape at N = 19 with a deformed Jπ = 1/2+ intruder state as a ground state, implying that 31Mg is part of the “island of inversion”. The collective properties of excited states were the subject of a Coulomb excitation experiment at REXISOLDE, CERN, employing a radioactive 31Mg beam. De-excitation γ -rays were detected by the MINIBALL γ -spectrometer in coincidence with scattered particles in a segmented Si-detector. The level scheme of 31Mg was extended. Spin and parity assignment of the 945 keV state yielded 5/2+ and its de-excitation is dominated by a strong collective M1 transition. Comparison of the transition probabilities of 30,31,32Mg establishes that for the N = 19 magnesium isotope not only the ground state but also excited states are largely dominated by a deformed pf intruder configuration.status: publishe

Electric quadrupole moments of the 2+_1 states in 100,102,104Cd

Using the REX-ISOLDE facility at CERN the Coulomb excitation cross sections for the 0+_gs → 2+_1 transition in the beta-unstable isotopes 100,102,104Cd have been measured for the first time. Two different targets were used, which allows for the first extraction of the static electric quadrupole moments Q(2+_1) in 102,104Cd. In addition to the B(E2) values in 102,104Cd, a first experimental limit for the B(E2) value in 100Cd is presented. The data was analyzed using the maximum likelihood method. The provided probability distributions impose a test for theoretical predictions of the static and dynamic moments. The data are interpreted within the shell-model using realistic matrix elements obtained from a G-matrix renormalized CD-Bonn interaction. In view of recent results for the light Sn isotopes the data are discussed in the context of a renormalization of the neutron effective charge. This study is the first to use the reorientation effect for post-accelerated short-lived radioactive isotopes to simultaneously determine the B(E2) and the Q(2+_1) values.status: publishe