A New Age of Biocatalysis Enabled by Generic Activation Modes.

Biocatalysis is currently undergoing a profound transformation. The field moves from relying on nature's chemical logic to a discipline that exploits generic activation modes, allowing for novel biocatalytic reactions and, in many instances, entirely new chemistry. Generic activation modes enable a wide range of reaction types and played a pivotal role in advancing the fields of organo- and photocatalysis. This perspective aims to summarize the principal activation modes harnessed in enzymes to develop new biocatalysts. Although extensively researched in the past, the highlighted activation modes, when applied within enzyme active sites, facilitate chemical transformations that have largely eluded efficient and selective catalysis. This advance is attributed to multiple tunable interactions in the substrate binding pocket that precisely control competing reaction pathways and transition states. We will highlight cases of new synthetic methodologies achieved by engineered enzymes and will provide insights into potential future developments in this rapidly evolving field.

Transition-metal catalyzed C-H activation as a means of synthesizing complex natural products.

Over the past few decades, the advent of C-H activation has led to a rethink among chemists about the synthetic strategies employed for multi-step transformations. Indeed, deploying innovative and masterful tricks against the numerous classical organic transformations has been the need of the hour. Despite this, the immense importance of C-H activation remains unfulfilled unless the methodology can be deployed for large-scale industrial processes and towards the concise, step-economic synthesis of prodigious natural products and pharmaceutical drugs. Lately, the growing potential of C-H activation methodology has indeed driven the pioneers of synthetic organic chemists into finding more efficient methods to accelerate the synthesis of such complex molecular scaffolds. This review aims to draw a general overview of the various C-H activation procedures that have been adopted for synthesizing these vast majority of structurally complicated natural products. Our objective lies in drawing a complete picture and taking the readers through the synthesis of a series of such complex organic compounds by simplified techniques, making it step-economic on a larger scale and thus instigating the readers to trigger the use of such methodology and uncover new, unique patterns for future synthesis of such natural products.