74630-47-0

Upstream product

• 111-66-0 oct-1-ene 
• 30089-00-0 9-octyl-9-bora-bicyclo[3.3.1]nonane 
• 13294-71-8 2-bromo-but-2-ene 
• 38972-70-2 (E)-3-methylundec-2-en-1-ol 
• 38841-98-4 n-octylmagnesium chloride 
• 3017-71-8 (E)-2-bromobut-2-ene 
• 3017-69-4 2-methyl-1-propenylbromide 
• 3017-68-3 (Z)-2-Bromo-2-butene 
• 629-27-6 1-Iodooctane 
• 5732-02-5 3-methylene-1-undecene 
• 693-54-9 Decan-2-one 
• 1754-88-7 ethylenetriphenylphosphorane 

Relevant academic research and scientific papers

Asymmetric Synthesis of Dihydropyranones via Gold(I)-Catalyzed Intermolecular [4+2] Annulation of Propiolates and Alkenes

Intermolecular asymmetric gold catalysis involving alkyne activation presents a significant challenge due to its distinct mechanistic mode from other metals. Herein, we report a highly enantioselective synthesis of α,β-unsaturated δ-lactones from [4+2] annulation of propiolates and alkenes in upto 95 percent ee. Notably, for the desired chiral recognition, the choice of 1,1,2,2-tetrachloroethane as solvent was found to be crucial. Furthermore, an anionic surfactant (sodium dodecyl sulfate) improved the product selectivity in the divergence of the cyclopropyl gold carbene intermediate.

Utilization of a Trimethylsilyl Group as a Synthetic Equivalent of a Hydroxyl Group via Chemoselective C(sp3)-H Borylation at the Methyl Group on Silicon

A conversion of trimethylsilylalkanes into the corresponding alcohols is established based on an iridium-catalyzed, chemoselective C(sp3)-H borylation of the methyl group on silicon. The (borylmethyl)silyl group formed by C(sp3)-H borylation is treated with H2O2/NaOH, and the resulting (hydroxymethyl)silyl group is converted into a hydroxyl group by Brook rearrangement, followed by oxidation of the resulting methoxysilyl group under Tamao conditions. An alternative route proceeding through the formylsilyl group formed from a (hydroxymethyl)silyl group by Swern oxidation is also established. The method is applicable to substituted trimethylsilylcycloalkanes and 1,1-dimethyl-1-silacyclopentane for conversion into the corresponding stereodefined cycloalkyl alcohols and 1,4-butanediol.

Copper(i)-catalysed asymmetric allylic reductions with hydrosilanes

A copper(i)-catalysed asymmetric allylic reduction enables a regio- and stereoselective transfer of a hydride nucleophile in an SN2′-fashion onto allylic bromides. This transformation represents a conceptually orthogonal approach to allylic substitution reactions with carbon nucleophiles. A copper(i) complex based upon a chiral N-heterocyclic carbene (NHC) ligand allows for stereoselectivity reaching 99% ee. The catalyst enables a stereoconvergent reaction irrespective of the double bond configuration of the starting materials.

Copper(I)-Catalyzed Allylic Substitutions with a Hydride Nucleophile

An easily accessible copper(I)/N-heterocyclic carbene (NHC) complex enables a regioselective hydride transfer to allylic bromides, an allylic reduction. The resulting aryl- and alkyl-substituted branched α-olefins, which are valuable building blocks for synthesis, are obtained in good yields and regioselectivity. A commercially available silane, (TMSO)2Si(Me)H, is employed as hydride source. This protocol offers a unified alternative to the established metal-catalyzed allylic substitutions with carbon nucleophiles, as no adaption of the catalyst to the nature of the nucleophile is required.

Copper-Catalyzed Regioselective Hydroalkylation of 1,3-Dienes with Alkyl Fluorides and Grignard Reagents

Copper complexes generated in situ from CuCl2, alkyl Grignard reagents, and 1,3-dienes play important roles as catalytic active species for the 1,2-hydroalkylation of 1,3-dienes by alkyl fluorides through C-F bond cleavage. The alkyl group is introduced to an internal carbon atom of the 1,3-diene regioselectively, thus giving rise to the branched terminal alkene product. Making the switch: A copper-hydride species, generated by the treatment of a copper salt with alkyl Grignard reagents, catalyzes the 1,2-hydroalkylation of 1,3-dienes by alkyl fluorides and Grignard reagents. The alkyl group of the alkyl fluoride is selectively introduced to an internal carbon atom of the 1,3-diene and the Grignard reagent acts as hydride source to give the branched terminal alkene, even in the presence of alkenes and alkynes.

Iron thiolate complexes: Efficient catalysts for coupling alkenyl halides with alkyl grignard reagents

Ironing out the kinks: Efficient new catalytic systems based on iron thiolates are described for the iron-catalyzed cross-coupling of alkyl Grignard reagents with alkenyl halides (see scheme). The reaction is highly chemo- and stereoselective. With this new procedure, the use of N-methylpyrrolidone as a co-solvent is no longer required. Copyright

An alternative regioselective ring-opening of epoxides to chlorohydrins mediated by chlorotitanium(IV) reagents

A regioselective cleavage of various epoxides to vic-chlorohydrin isomers by using TiCl4 or TiCl4-Ti(O-i-Pr)4 complex was investigated. The less substituted alcohols, C2-attack products, were formed by the use of TiCl4 in CH2Cl2. On the other hand, the less substituted chlorides, Cl-attack products, were formed by using TiCI(O-i-Pr)3 in DMF. These regioselectivities depend on both the acidity of the Lewis acids and the polarity of the solvents.

Highly stereo and chemoselective iron-catalyzed alkenylation of organomagnesium compounds

In the presence of Fe(acac)3, Grignard reagents react readily with alkenyl halides (X = I, Br or Cl) in a THF/NMP mixture to give the cross-coupling products in high yields with an excellent stereoselectivity (≤99.5%). The scope of the reaction is very broad since a vast array of functional groups are tolerated (esters, nitriles, aromatic or aliphatic halides and even ketones). The procedure reported herein is an interesting alternative to the classical Pd- or Ni-catalyzed reactions, especially for preparative organic chemistry.

Palladium-Catalyzed Inter- and Intramolecular Cross-Coupling Reactions of B-Alkyl-9-borabicyclononane Derivatives with 1-Halo-1-alkenes or Haloarenes. Syntheses of Functionalized Alkenes, Arenes, and Cycloalkenes via a Hydroboration-Coupling Sequence

The cross-coupling reaction of B-alkyl-9-borabicyclononanes (B-R-9-BBN), readily obtainable from alkenes by hydroboration, with 1-halo-1-alkenes or haloarenes in the presence of a catalytic amount of PdCl2(dppf) and bases, such as sodium hydroxide, potassium carbonate, and phosphate, gave the corresponding alkenes or arenes.Because the reaction is tolerant of a variety of functionalities on either coupling partner, stereochemically pure functionalized alkenes and arenes can be obtained under mild conditions.The utility of the reaction was demonstrated by the stereoselective synthesis of 1,5-alkadienes (7 and 8) and the extension of a side chain in a steroid (11).The hydroboration of haloalkadienes (12), followed by the intramolecular cross-coupling, gave a short-step procedure for synthesis of cycloalkenes, benzo-fused cycloalkenes, and exocyclic alkenes (14 and 16).

PALLADIUM-CATALYZED CROSS-COUPLING REACTIONS OF B-ALKYL-9-BBN OF TRIALKYLBORANES WITH ARYL AND 1-ALKENYL HALIDES

The reactions of trialkylboranes or B-alkyl-9-BBN with aryl and 1-alkenyl halides take place readily in the presence of PdCl2(dppf) and sodium hydroxide or methoxide to afford alkylatad arenes and alkenes in excellent yields.