13027-73-1

Upstream product

• 110-82-7 cyclohexane 
• 22979-35-7 Methyl phenyldiazoacetate 
• 60-29-7 diethyl ether 
• 3469-00-9 methyl 2,2-diphenylacetate 
• 64-17-5 ethanol 
• 76-89-1 methyl benzilate 
• 67-56-1 methanol 
• 86769-71-3 Methyl α-(cyclohex-2-enyl)-α-phenylacetate 
• 15206-55-0 methyl 2-oxo-2-phenylacetate 
• 1735-17-7 Cyclohexane-d12 
• 623-73-4 diazoacetic acid ethyl ester 
• 6632-43-5 methyl α-acetoxy-α-phenylbenzeneacetate 
• 40195-27-5 (1-methoxy-2-phenylvinyloxy)trimethylsilane 
• 110-83-8 cyclohexene 

Downstream Products

• 4442-83-5 2-cyclohexyl-2-phenylethan-1-ol 

Relevant academic research and scientific papers

Effect of carbenoid structure on the reactivity of rhodium-stabilized carbenoids

The outcome of rhodium(II) pivalate catalyzed decomposition of diaozoacetates in the presence of cyclohexane is highly dependent on carbenoid structure. Carbenoids derived from phenyldiazoacetates or diazoketoesters undergo high yielding intermolecular C-H insertions while other carbenoid systems undergo rearrangements, dimerization or trimerization.

Catalytic C(sp3)-H alkylation via an iron carbene intermediate

The catalytic transformation of a C(sp3)-H bond to a C(sp3)-C bond via an iron carbene intermediate represents a long-standing challenge. Despite the success of enzymatic and small molecule iron catalysts mediating challenging C(sp3)-H oxidations and aminations via high-valent iron oxos and nitrenes, C(sp3)-H alkylations via isoelectronic iron carbene intermediates have thus far been unsuccessful. Iron carbenes have been inert, or shown to favor olefin cyclopropanation and heteroatom-hydrogen insertion. Herein we report an iron phthalocyanine-catalyzed alkylation of allylic and benzylic C(sp3)-H bonds. Mechanistic investigations support that an electrophilic iron carbene mediates homolytic C-H cleavage and rebounds from the resulting organoiron intermediate to form the C-C bond; both steps are tunable via catalyst modifications. These studies suggest that for iron carbenes, distinct from other late metal carbenes, C-H cleavage is partially rate-determining and must be promoted to effect reactivity.

Blue light-promoted photolysis of aryldiazoacetates

Aryldiazoacetates can undergo photolysis under blue light irradiation (460-490 nm) at room temperature and under air in the presence of numerous trapping agents, such as styrene, carboxylic acids, amines, alkanes and arenes, thus providing a straighforward and general platform for their mild functionalization.

Iron-Catalyzed Carbenoid Insertion into C(sp 3)-H Bonds

An iron-catalyzed carbenoid insertion into C-H bonds of alkanes was developed with high activity (turnover numbers up to 690 in a gram-scale experiment) and chemoselectivity. This non-heme iron-catalyzed C(sp 3)-H insertion reaction provides an efficient strategy for C-H functionalization.

Highly Regio- and Enantioselective Formal [3 + 2]-Annulation of Indoles with Electrophilic Enol Carbene Intermediates

Chiral cyclopentane-fused indolines are synthesized with high regio- and enantiocontrol by formal [3 + 2]-annulation reactions of indoles and electrophilic enol carbenes. High enantioselectivity and exclusive regiocontrol occurred with enoldiazoacetamides using a less sterically encumbered prolinate-ligated dirhodium(II) catalyst in reactions with N-substituted indoles without substituents at the 2- or 3-positions via a selective vinylogous addition process. In this transformation, donor-acceptor cyclopropenes generated from enoldiazoacetamides serve as the carbene precursors to form metal carbene intermediates.

C-H insertion catalyzed by tetratolylporphyrinato methyliridium via a metal-carbene intermediate

C-H insertion reactions between different substrates and diazo reagents were catalyzed by tetratolylporphyrinato methyliridium (Ir(TTP)CH3). The highest yields were achieved for reactions between the bulky diazo reagent methyl 2-phenyldiazoacet

Ruthenium Catalysts and Uses Thereof

Ruthenium nanoparticles supported on non-cross-linked soluble polystyrene were prepared by reacting [RuCl2(C6H5CO2Et)]2 with polystyrene in open air. They effectively catalyze intra- and intermolecular carbenoid insertion into C—H and N—H bonds, alkene cyclopropanation, and ammonium ylide/[2,3]-sigmatropic rearrangement reactions. This supported ruthenium catalyst is much more reactive than [RuCl2(p-cymene)]2 and Ru(Por)CO] for catalytic intermolecular carbenoid C—H bond insertion into saturated alkanes. By using a-diazoacetamide as a substrate for intramolecular carbenoid C—H insertion, the supported ruthenium catalyst can be to recovered and reused for ten successive iterations without significant loss of activity.

Highly selective metal catalysts for intermolecular carbenoid insertion into primary C-H bonds and enantioselective C-C bond formation

(Figure Presented) Primary C-H bond activation! A Rh complex of bis-pocket porphyrin I catalyzes carbenoid insertion into the C-H bonds of n-alkanes with a primary/secondary selectivity (per C-H bond) of up to 11.4:1 (see picture). Enantioselective secondary C-H bond functionalization catalyzed by a Rh complex of Halterman's chiral porphyrin features up to 93% ee. These reactions exhibit up to 6477 turnovers after the catalyst was recycled five times.

Intermolecular cyclopropanation versus CH insertion in Rh(II)-catalyzed carbenoid reactions

The product ratio of intermolecular insertion and cyclopropanation in transition metal-catalyzed diazo decompositions depends strongly upon the metal, its ligands and upon the substituents of the diazo compound. Ethyl diazoacetate (2a) reacts with cyclohexene (1) almost exclusively by cyclopropanation. However, diazomalonate (2d) and methyl 2-diazophenylacetate (2e) in the presence of Rh(II) catalysts exhibit a marked tendency towards allylic CH insertion. With 1,4-cyclohexadiene (6), methyl 2- diazophenylacetate (2e) in the presence of chiral Rh(II) catalysts affords the allylic insertion product 7 in almost quantitative yield and with up to 74% ee. (C) 2000 Elsevier Science Ltd.