We demonstrate here a seed-directed synthesis (SDS) of Beta, Levyne, and Heulandite zeolites in the absence of organotemplates, where the seeds drive crystallization of the zeolites. Compared with conventional Beta synthesized in the presence of organic templates, Beta-SDS exhibits large textural parameters, stable Al species, and unprecedentedly high density of active sites, resulting in superior catalytic activity and selectivity for valuable products in catalysis.

Exploring multistep cascade reactions triggered by C−H activation are recognized as appealing, yet challenging. Herein, we disclose a Rh(III)-catalyzed domino C−H coupling of N-carbamoyl indoles and 4-hydroxy-2-alkynoates for the streamlined assembly of highly functionalized furan-2(5H)-ones in which the carbamoyl-directing group (DG) is given a dual role of an auxiliary group and a migrating acylating reagent via the cleavage of stable C−N bonds at room temperature. More importantly, the obtained furan-2(5H)-one skeleton could be further functionalized under air in situ via C5−H hydroxylation by simply switching the solvent or additive, providing fully substituted furan-2(5H)-ones with the installation of an alcohol-based C 5 quaternary carbon center. Detailed experimental studies and density functional theory calculations reveal that a Rh(III)-mediated tandem C−H activation/alkyne insertion/DG migration/lactonization accounts for the developed transformation to achieve high functionalities with the observed exclusive selectivity. The potential biological application of the obtained furan-2(5H)-ones as a class of potent PPARγ ligands further highlights the synthetic utility of the developed methodology. This protocol is endowed with several salient features including efficient multistep cascade triggered by C−H activation, excellent chemo-, regio-, and stereoselectivity, high bondforming efficiency (e.g., two C−C and two C−O bonds), solvent-or additive-controlled product selectivity, good functional-group compatibility, and mild redox-neutral conditions.

Herein, we report the divergent synthesis of alkynylated imidazo­[1,5-a]­indoles and α,α-difluoromethylene tetrasubstituted alkenes through Rh­(III)-catalyzed [4 + 1] annulation/alkyne moiety migration and C–H alkenylation/DG migration, respectively. This protocol features tunable product selectivity, excellent chemo-, regio-, and stereoselectivity, broad substrate scope, moderate to high yields, good tolerance of functional groups, and mild redox-neutral conditions.

We have achieved an Ir(III)-catalyzed temperaturecontrolled divergent synthesis of tetrasubstituted alkenes and pyrrolo[1,2-a]indole derivatives through CÀ H alkenylation/DG migration and [3 + 2] annulation, respectively. This method has various advantageous features: a) excellent regio-and stereoselectivity and good functional group tolerance, b) broad substrate scope and moderate to excellent yields, c) mild redox-neutral reaction conditions and operational simplicity.

Chiral β-hydroxysulfides are an important class of organic compounds which find broad application in organic and pharmaceutical chemistry. Herein we describe the development of novel biocatalytic and chemoenzymatic methods for the enantioselective synthesis of β-hydroxysulfides by exploiting ketoreductase (KRED) enzymes. Four KREDs were discovered from a pool of 384 enzymes identified and isolated through a metagenomic approach. KRED311 and KRED349 catalysed the synthesis of β-hydroxysulfides bearing a stereocentre at the CÀ O bond with opposite absolute configurations and excellent ee values by novel chemoenzymatic and biocatalytic-chemical-biocatalytic (bio-chem-bio) cascades starting from commercially available thiophenols/thiols and α-haloketones/alcohols. KRED253 and KRED384 catalysed the enantioselective synthesis of β-hydroxysulfides bearing a stereocentre at the CÀ S bond with opposite enantioselectivities by dynamic kinetic resolution (DKR) of racemic α-thioaldehydes.