86429-26-7

Upstream product

• 917-92-0 3,3-Dimethylbut-1-yne 
• 3677-81-4 diphenylboronchloride 
• 5123-17-1 bromodiphenylborane 
• 189025-08-9 3,3-Dimethyl-2-phenyl-1-butanol 
• 107847-16-5 (+/-)-2-(1,1-dimethylethyl)-2-phenyloxirane 
• 938-16-9 2,2-dimethylpropiophenone 
• 591-51-5 phenyllithium 
• 21811-48-3 3,3-dimethyl-2-phenyl-butan-2-ol 
• 75-97-8 3,3-dimethyl-butan-2-one 
• 136175-22-9 2-tert-butyl-2-phenyl-1-(4-tolylsulfonyl)aziridine 
• 5676-29-9 (3,3-dimethylbut-1-en-2-yl)benzene 

Downstream Products

• 107847-33-6 (5SR,6SR)-5-hydroxy-2,2,7,7-tetramethyl-6-phenyloctan-3-one 
• 107847-33-6 (5RS,6SR)-5-hydroxy-2,2,7,7-tetramethyl-6-phenyloctan-3-one 
• 114245-64-6 (E)-(6RS)-2,2,7,7-tetramethyl-6-phenyloct-4-en-3-one 
• 114245-65-7 (E)-(4RS)-5,5-dimethyl-1,4-diphenylhex-2-en-1-one 
• 938-16-9 2,2-dimethylpropiophenone 
• 1198158-13-2 2-fluoro-3,3-dimethyl-2-phenylbutyraldehyde 

Relevant academic research and scientific papers

An air-stable cationic iridium hydride as a highly active and general catalyst for the isomerization of terminal epoxides

We describe the use of an air-stable iridium hydride catalyst for the isomerization of terminal epoxides into aldehydes with perfect regioselectivity. The system operates at low loadings of catalyst (0.5 mol%), is highly practical, scalable, and tolerates functional groups that would not be compatible with Lewis acids typically used in stoichiometric amounts. Evidence for a rare hydride mechanism are provided. This journal is the Partner Organisations 2014.

Complementary catalytic strategies to access α-chiral aldehydes

The present article summarizes the development of two novel and complementary catalytic methods to access α-chiral aldehydes. A C1-symmetric chiral (P,N) ligand with a structure derived from the ubiquitous binepine scaffold has been specifically designed for the Pd-catalyzed α arylation of aldehydes to access indane derivatives with a well-defined quaternary stereocenter in high yields and excellent enantioselectivities. In addition, a dinuclear palladium hydride catalyst has been synthesized for the isomerization of terminal and trisubstituted epoxides into aldehydes and ketones respectively. Combined experimental and theoretical investigations pointed to an unprecedented 'epoxide-opening/hydride-transfer' sequence. The mechanism also features two distinct enantio-determining steps in the kinetic resolution of racemic epoxides. Schweizerische Chemische Gesellschaft.

Isomerization of terminal epoxides by a [Pd-H] catalyst: A combined experimental and theoretical mechanistic study

An unusual palladium hydride complex has been shown to be a competent catalyst in the isomerization of a variety of terminal and internal epoxides. The reaction displayed broad scope and synthetic utility. Experimental and theoretical evidence are provided for an unprecedented hydride mechanism characterized by two distinct enantio-determining steps. These results hold promise for the development of an enantioselective variant of the reaction.

Reactions of a Tertiary Carbon Carrying a tert-Butyl Group: Acid-Catalyzed Alcoholyses of Activated Aziridines without and with Solvent Assistance

Acid-catalyzed ring opening of tosylated and acylated 2-tert-butylaziridines 1 (2-phenyl) and 2 (2-benzyl) generates carbenium ions 18 (from 1) and 19 (from 2) which rearrange by a neopentyl rearrangement to carbenium ions 20 (18 -> 20) and 21 (19 -> 21).Reactions of 18-21 form the final products: (1) deprotonation yields allylamides, homoallylamides, and enamides; (2) external trapping of 18 or 19 by a solvent molecule yields ethers; (3) internal trapping (only acylated 1 and 2) yields oxazolines and dihydrooxazines.The amount of external trapping with 1a,b depends on the activation: 1a (tosyl activation) yields more methyl ether (75percent vs 51percent) than 1b (benzoyl), but 1a yields less isopropyl ether (0percent vs 25percent) than 1b.The latter finding is in accord with an intramolecular interaction of the carbenium center of 18a with one of the tosyl oxygen atoms provided that this interaction distorts the carbenium plane to a pyramid which sterically retards external trapping.The former finding is not observed with 2a and 2b.This points to at least some methanol-assisted ring opening of 1a-H(+) that must be supported by a benzylic effect.The required conformation of the phenyl ring is fixed in 1a-H(+) (N-protonation and bulky SO2 cis to phenyl) but not in 1b-H(+) (O-protonation and planar nitrogen conformation).

Efficient Wittig-Horner Synthesis of Acyclic α-Enones with an Asymmetric Carbon at the γ-Position Using Barium Hydroxide

β-Monosubstituted acyclic α-enones with an asymmetric carbon at the γ-position: (E)-(5RS)-5-phenylhex-3-en-2-one, (4a), (E)-(6RS)-2,2-dimethyl-6-phenylhept-4-en-3-one, (4b), (E)-(4RS)-1,4-diphenylpent-2-en-1-one, (4c), (E)-(5RS)-6,6-dimethyl-5-phenylhept-

Boration Reactions with 1-Alkynes

Halodiorganoboranes R2BHal(R = Et, Ph) as well as benzyldihaloboranes PhCH2BHal2 undergo a regiospecific addition to the triple-bond of 1-alkynes ACCR'.The reversible haloboration (1) gives Z-alkenes as the more stable isomers.At elevated temperatures, the irreversible 1,1-organoboration (2) predominates, accompanied by a 1,2-transfer of A, whereas the 1,2-organoboration (3) is observed only as an unimportant side-reaction in a few cases.The cyclisation (4) occurs as a sequence of cis-haloboration and intramolecular aromatic alkenylation in the case of PhCH2BCl2 as borating agent.