Kinetic Resolution in Transannular Morita-Baylis-Hillman Reaction: An Approximation to the Synthesis of Sesquiterpenes from Guaiane Family

An approximation to the synthesis of several sesquiterpenes from the Guaiane family is described in which the core structure was obtained through a transannular Morita-Baylis-Hillman reaction performed under kinetic resolution. Several manipulations of the obtained MBH adduct have been carried out directed towards the total synthesis of γ-Gurjunene, to the formal synthesis of Clavukerin A, to the synthesis of a non-natural isomer of isoguaiane and to the synthesis of an advanced intermediate in the total synthesis of Palustrol.

Steady-State Planning in Expected Reward Multichain MDPs

The planning domain has experienced increased interest in the formal synthesis of decision-making policies. This formal synthesis typically entails finding a policy which satisfies formal specifications in the form of some well-defined logic. While many such logics have been proposed with varying degrees of expressiveness and complexity in their capacity to capture desirable agent behavior, their value is limited when deriving decision-making policies which satisfy certain types of asymptotic behavior in general system models. In particular, we are interested in specifying constraints on the steady-state behavior of an agent, which captures the proportion of time an agent spends in each state as it interacts for an indefinite period of time with its environment. This is sometimes called the average or expected behavior of the agent and the associated planning problem is faced with significant challenges unless strong restrictions are imposed on the underlying model in terms of the connectivity of its graph structure. In this paper, we explore this steady-state planning problem that consists of deriving a decision-making policy for an agent such that constraints on its steady-state behavior are satisfied. A linear programming solution for the general case of multichain Markov Decision Processes (MDPs) is proposed and we prove that optimal solutions to the proposed programs yield stationary policies with rigorous guarantees of behavior.

Efficient access to aliphatic esters by photocatalyzed alkoxycarbonylation of alkenes with alkyloxalyl chlorides

Aliphatic esters are essential constituents of biologically active compounds and versatile chemical intermediates for the synthesis of drugs. However, their preparation from readily available olefins remains challenging. Here, we report a strategy to access aliphatic esters from olefins through a photocatalyzed alkoxycarbonylation reaction. Alkyloxalyl chlorides, generated in situ from the corresponding alcohols and oxalyl chloride, are engaged as alkoxycarbonyl radical fragments under photoredox catalysis. This transformation tolerates a broad scope of electron-rich and electron-deficient olefins and provides the corresponding β-chloro esters in good yields. Additionally, a formal β-selective alkene alkoxycarbonylation is developed. Moreover, a variety of oxindole-3-acetates and furoindolines are prepared in good to excellent yields. A more concise formal synthesis of (±)-physovenine is accomplished as well. With these strategies, a wide range of natural-product-derived olefins and alkyloxalyl chlorides are also successfully employed.