ConspectusVicinal diamines are important structural motifs present in various biologically and chemically significant molecules. Direct diamination of olefins provides an effective approach to this class compounds. Unlike well-established oxidation processes such as epoxidation, dihydroxylation, aminohydroxylation, direct had remained a long-standing challenge been less well developed.In Account, we summarize our recent studies on Pd(0)- Cu(I)-catalyzed diaminations using...

ConspectusThe use of frustrated Lewis pairs is an extremely important approach to metal-free hydrogenations. In contrast the rapid growth catalytic reactions, asymmetric hydrogenations are far less developed due a severe shortage readily available chiral pair catalysts with high activities and selectivities. Unlike stable base component pairs, moisture-sensitive boron acid difficult prepare. The development convenient methods for quick construction acids therefore great interest.In this...

This paper describes a highly enantioselective metal-free hydrogenation of imines using chiral dienes as "ligands" for the generation catalysts with HB(C6F5)2 by hydroboration in situ to furnish variety amines up 89% ee, which provides practical strategy development novel frustrated Lewis pairs asymmetric hydrogenation.

This paper describes a catalytic asymmetric diamination process for terminal olefins at allylic and homoallylic carbons via formal C−H activation using di-tert-butyldiaziridinone as nitrogen source with catalyst generated from Pd2(dba)3 chiral phosphorus amidite ligand. A wide variety of readily available can be effectively diaminated in good yields high regio-, diastereo-, enantioselectivities.

This paper describes a catalytic asymmetric diamination process using di-tert-butyldiaziridinone as nitrogen source with catalyst generated from Pd2(dba)3 and chiral phosphorus amidite ligand. A wide variety of conjugated dienes triene can be effectively diaminated in good yields high regio-, diastereo-, enantioselectivities.

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Using a simple combination of tri-tert-butylphosphine and chiral borane generated in situ by the hydroboration diene with HB(C6F5)2 as frustrated Lewis pair catalyst, highly enantioselective metal-free hydrogenation silyl enol ethers was successfully realized to furnish variety optically active secondary alcohols 93-99% yields 88->99% ee's.

Abstract A wide range of 2,3‐disubstituted quinoxalines have been successfully hydrogenated with H 2 using borane catalysts to produce the desired tetrahydroquinoxalines in 80–99 % yields excellent cis selectivity. Significantly, asymmetric reaction employing chiral generated by situ hydroboration dienes HB(C 6 F 5 ) under mild conditions has also achieved up 96 ee , and represents first catalytic system furnish optically active ‐2,3‐disubstituted 1,2,3,4‐tetrahydroquinoxalines.

This paper describes a novel diamination process of terminal olefins at allylic and homoallylic carbons via formal C−H activation using di-tert-butyldiaziridinone as nitrogen source Pd(PPh3)4 catalyst. A wide variety can be effectively diaminated in good yields with high stereoselectivity.

Inspired by the zwitterion species generated from splitting of H2 frustrated Lewis pairs, we put forward a novel pair combination Hδ- and Hδ+ incorporated acid base together. Piers' borane chiral tert-butylsulfinamide were chosen as FLP, metal-free asymmetric transfer hydrogenation imines was realized with high enantioselectivities. Significantly, ammonia hydrogen source, catalytic reaction using 10 mol % borane, tert-butylsulfinamide, pyridine additive, has been successfully achieved to...

A metal-free direct hydrogenation of pyridines was successfully realized by using homogeneous borane catalysts generated from alkenes and HB(C6F5)2 via in situ hydroboration. The reaction affords a broad range piperidines high yields with excellent cis stereoselectivities.

Various dienes and a triene can be regioselectively diaminated at the internal double bond with good yields high diastereoselectivity using di-tert-butyldiaziridinone (5) as nitrogen source Pd(PPh3)4 (1−10 mol %) catalyst. Kinetic studies 1H NMR spectroscopy show that diamination is first-order in total Pd catalyst inverse PPh3. For reactive dienes, such 1-methoxybutadiene (6g) alkyl 1,3-butadienes (6a, 6j), zero-order olefin. olefins relatively low reactivity, (E)-1-phenylbutadiene (6b)...

A highly enantioselective hydrosilylation of 1,2-dicarbonyl compounds was successfully realized for the first time utilizing combination tricyclohexylphosphine and chiral alkenylborane derived in situ from diyne as a frustrated Lewis pair catalyst. variety optically active α-hydroxy ketones esters were obtained 52-98% yields with 86-99% ee's.

The activation of H2 for the catalytic hydrogenation unsaturated compounds is one most useful reactions in both academia and chemical industry, which has long been predominated by transition-metal catalysis. However, metal-free hydrogen represents a formidable challenge, less developed. recent emerging chemistry frustrated Lewis pairs (FLPs) with combination sterically encumbered acids bases provides promising approach due to their amazing abilities challenging activation. In past several...

Abstract Chiral olefins have recently emerged as among the most promising ligands for asymmetric catalysis. In past nearly ten years, significant advances been made in developing ligands, including diene and heteroatom/olefin hybrid exploring their applications challenging metal‐catalyzed reactions. Especially some cases, chiral olefin an obvious advantage over conventional terms of activity selectivity. Besides often studied rigidly bicyclic dienes, readily accessible chiral‐chain dienes...

A variety of chiral binaphthyl-based terminal-alkene-phosphine hybrid ligands were synthesized in four steps with (S)-BINOL as a starting material and utilized for the Pd-catalyzed enantioselective allylic alkylations indoles pyrroles to afford desired products high yields good excellent ee's.

A palladium-catalyzed asymmetric allylic alkylation of 3-substituted indoles using P/olefin ligands was successfully achieved to afford a variety indolenines containing quaternary carbon stereocenter in high yields with up 87% ee. Significantly, this reaction provides concise access stereoisomer the natural product Angelicastigmin.

A metal-free hydrogenation of 2,4-disubstituted quinolines was realized for the first time using chiral diene derived borane catalysts to furnish corresponding tetrahydroquinolines in 75–98% yields with 95/5−99/1 dr's and 86–98% ee's. This catalytic system also effective 2,3-disubstituted give moderate good

A highly enantioselective cis-hydrogenation of 2,3,4-trisubstituted quinolines has been realized for the first time using chiral borane catalysts generated in situ from dienes. variety tetrahydroquinoline derivatives containing three contiguous stereogenic centers were obtained 76–99% yields with 82–99% ee's.

The first catalytic enantioselective hetero-Diels-Alder reaction between Brassard's diene and aldehydes has been achieved through hydrogen-bonding activation using TADDOL derivatives as catalysts to afford the corresponding delta-lactone in moderate-to-good yields with high enantioselectivities (up 91 % ee). reactions can be carried out either under solvent-free conditions or toluene. On basis of absolute configurations products interaction pattern...

Abstract An efficient asymmetric catalyst relies on the successful combination of a large number interrelated variables, including rational design, intuition, persistence, and good fortune—not all which are necessarily well‐understood; this renders such practice largely empirical. As result, possibility using combinatorial chemistry methods in catalysis research has been widely recognized to be highly desirable. In account, we attempt show principle application approach discovery chiral...

A dynamic diamination: The title transformation has been developed with diaziridine 1 as the nitrogen source (see scheme; dba=trans,trans-dibenzylideneacetone). reaction proceeds through an allylic amination and subsequent cyclization, a variety of terminal olefins can be effectively diaminated high regioselectivity.

A Cu(I)-catalyzed asymmetric diamination for a variety of conjugated dienes and triene with encouraging ee’s has been effectively achieved using (R)-DTBM-SEGPHOS as chiral ligand di-tert-butyldiaziridinone the nitrogen source.

This paper describes a novel intermolecular diamination process with CuCl as catalyst and di-tert-butylthiadiaziridine 1,1-dioxide nitrogen source. A variety of activated terminal olefins can be effectively diaminated in good yields under mild reaction conditions.

This paper describes a novel intermolecular alpha-amination process of esters using CuCl as catalyst and di-tert-butyldiaziridinone nitrogen source. A variety hydantoins can be formed effectively under mild reaction conditions.