176436-85-4

Upstream product

• 3757-88-8 tributylstannylethynylbenzene 
• 2043-61-0 cyclohexanecarbaldehyde 
• 536-74-3 phenylacetylene 
• 16616-46-9 1-cyclohexyl-3-phenylprop-2-yn-1-one 
• 130708-23-5 1-cyclohexyl-3-phenylprop-2-yn-1-ol 
• 58458-85-8 trimethoxy(phenylethynyl)silane 
• 557-20-0 diethylzinc 

Downstream Products

• 1428337-72-7 C₁₉H₂₄O 
• 1428337-96-5 C₁₉H₂₄O 
• 1342340-86-6 N-[(Z)-2-bromo-3-phenylprop-2-enyl]-N-[(1R)-1-cyclohexyl-3-phenylprop-2-ynyl]-4-methylbenzenesulfonamide 
• 1342340-64-0 (1R)-1-cyclohexyl-2-(4-methylphenylsulfonyl)-9-phenyl-2,3-dihydro-1H-benzo[f]isoindole 
• 1342341-20-1 N-[(1R)-1-cyclohexyl-3-phenylprop-2-ynyl]-4-methylbenzenesulfonamide 

Relevant academic research and scientific papers

Highly enantioselective alkynylation of aldehydes catalyzed by a readily available chiral amino alcohol-based ligand

A new inexpensive chiral amino alcohol-based ligand, (1S,2S)-2-N,N-dimethylamino-1-(p-nitrophenyl)-3-(t-butyl-dimethylsilyloxy) propane-1-ol, was developed for the asymmetric alkynylation of aliphatic and aromatic aldehydes, to prepare the corresponding propargylic alcohols in high yields with up to 99% ee.

Development of Novel Chloramphenicol Scaffold-Based Chiral Hydroxyl Oxazoline Ligands and Their Application to the Asymmetric Alkynylation of Isatins

The synthesis of new chloramphenicol base-derived chiral hydroxyl oxazoline ligands, and their use in the first Zn(OTf)2-catalyzed enantioselective alkynylation of isatins are described. This transformation features mild reaction conditions, a remarkably broad substrate scope, and excellent functional group tolerance, affording the corresponding tertiary propargylic alcohols in high yields and with high enantioselectivities. The application of chiral hydroxyl oxazolines as ligands in Zn(II)-catalyzed asymmetric alkynylation reactions is unprecedented. (Figure presented.).

Asymmetric addition of phenylacetylene to aldehydes catalyzed by complex of O-sulfonyl camphor derivatives and titanium

Several novel ligands that are based on the camphor skeleton or contain the O-sulfonyl group were synthesized and used in the asymmetric addition of phenylacetylene to aldehydes. This enantioselective reaction afforded chiral propargylic alcohols in high

Enantioselective Alkyne Addition to Aliphatic, Aromatic, and Vinyl Aldehydes Using Zn, iPrI, H8BINOL, and Ti(OiPr)4

A new catalytic system based on the readily available Zn, iPrI, H8BINOL, and Ti(OiPr)4 has been developed which avoids the use of pyrophoric ZnEt2. It can effectively catalyze the reaction of various terminal alkynes with aromatic, aliphatic, and vinyl aldehydes to generate chiral propargylic alcohols at room temperature with up to 98% yield and 98% enantiomeric excess. This new system signifciantly expands the substrate scope of the previously reported system using Zn, EtI, BINOL, and Ti(OiPr)4.

Lithium binaphtholate-catalyzed asymmetric addition of lithium acetylides to carbonyl compounds

The asymmetric addition of lithium acetylides to carbonyl compounds in the presence of a chiral lithium binaphtholate catalyst was developed. A procedure involving the slow addition of carbonyl compounds to lithium acetylides improved the enantioselectivi

Utilization of whole cell mediated deracemization in a chemoenzymatic synthesis of enantiomerically enriched polycyclic chromeno[4,3-b] pyrrolidines

Various aryl and alkyl substituted optically pure propargyl alcohols were obtained with excellent ee (up to >99%) and isolated yields (up to 87%) by deracemization using whole cells of Candida parapsilosis ATCC 7330. The whole cells show substrate specificity towards alkyl substituted propargyl alcohols and a switch in the enantioselectivity has been observed from 'R' to 'S' upon increasing the chain length. For the first time, enantiopure (R)-4-(3-hydroxybut-1-ynyl)benzonitrile, (R)-4-(biphenyl-4-yl)but-3-yn-2-ol, (S)-ethyl 3-hydroxy-5-phenylpent-4-ynoate and (S)-4-phenylbut-3-yne-1,2-diol were obtained using this strategy. Optically pure propargyl alcohol thus obtained was used as a chiral starting material in the synthesis of enantiomerically enriched poly-substituted pyrrolidines and a pyrrole derivative successfully demonstrating a chemoenzymatic route. This journal is

3-Aminoquinazolinones as chiral ligands in catalytic enantioselective diethylzinc and phenylacetylene addition to aldehydes

A series of readily known enantiomerically pure 3-aminoquinazolinones 1a-d were synthesised from easily accessible chiral pool α-hydroxy acids and α-amino acids in only four steps without any requirement of chromatography. These quinazolinones were examined as chiral ligands for catalytic enantioselective diethylzinc and phenylacetylene additions to aldehydes. For enantioselective alkylations, the effects of temperature, solvent, diethylzinc and ligand criteria were analysed, and the desired chiral alcohols were obtained in up to 86% ee. 3-Aminoquinazolinones 1a-d were also shown to be very useful ligands in enantioselective alkynylations of aldehydes. Based upon the optimised conditions, the corresponding propargylic alcohols were obtained in up to 94% ee.

Synthesis of quinazoline based chiral ligands and application in the enantioselective addition of phenylacetylene to aldehydes

Five novel 4-phenylquinazolinols were synthesised in three steps. Their application as ligands in the titanium tetraisopropoxide promoted catalytic enantioselective addition of phenylacetylene to a variety of aldehydes gave propargylic alcohols. Under the

Cooperative catalysis of metal and O-H...O/sp3-C-H...O two-point hydrogen bonds in alcoholic solvents: Cu-catalyzed enantioselective direct alkynylation of aldehydes with terminal alkynes

Catalyst-substrate hydrogen bonds in artificial catalysts usually occur in aprotic solvents, but not in protic solvents, in contrast to enzymatic catalysis. We report a case in which ligand-substrate hydrogen-bonding interactions cooperate with a transition-metal center in alcoholic solvents for enantioselective catalysis. Copper(I) complexes with prolinol-based hydroxy amino phosphane chiral ligands catalytically promoted the direct alkynylation of aldehydes with terminal alkynes in alcoholic solvents to afford nonracemic secondary propargylic alcohols with high enantioselectivities. Quantum-mechanical calculations of enantiodiscriminating transition states show the occurrence of a nonclassical sp3-C-H...O hydrogen bond as a secondary interaction between the ligand and substrate, which results in highly directional catalyst-substrate two-point hydrogen bonding. Efficient enantioselective direct carbonyl addition of terminal alkynes is achieved through ligand-substrate two-point hydrogen bonds consisting of O-H...O and sp3-C-H...O interactions that cooperate with copper in alcoholic solvents (see picture). Copyright

Synthesis of 1,3-aminonaphthols by diastereoselective Betti-type aminoalkylation of dihydroxy naphthalenes; Diastereoselectivity, absolute configuration, and application

Dihydroxy naphthalenes have been applied in Betti-type solventless condensation between aldehydes and (S)-phenylethylamine as a chiral auxiliary. A series of chiral 1,3-aminonaphthols has been synthesized and isolated in diastereoisomerically pure form. The absolute configurations of the aminonaphthols synthesized have been determined by means of advanced NMR experiments and confirmed by X-ray crystallography. The new chiral aminonaphthols have been tested as pre-catalysts for the addition of diethyl zinc and alkynyl-Zn-reagents to aldehydes with enantioselectivities of up to 98% ee.