33083-81-7

Upstream product

• 109-72-8 n-butyllithium 
• 618-36-0 rac-methylbenzylamine 
• 16659-09-9 1-phenylbutylideneamine 
• 917-54-4 methyllithium 
• 591-51-5 phenyllithium 
• 220263-66-1 2-Methyl-propane-2-sulfinic acid ((S)-1-methyl-1-phenyl-pentyl)-amide 
• 100-47-0 benzonitrile 
• 103794-57-6 (R)-O-methyl-N-(α-methylbenzyl)hydroxylamine 
• 24716-16-3 2-Phenyl-2-methylhexylisocyanat 

Downstream Products

• 36789-53-4 N-((S)-1-methyl-1-phenyl-pentyl)-benzamide 
• 20826-49-7 trans-hex-2-en-2-ylbenzene 
• 20826-50-0 (Z)-hex-2-en-2-ylbenzene 
• 20826-78-2 N-Acetyl-α-methyl-α-butyl-benzylamin 
• 36789-53-4 (+/-)-N-(1-methyl-1-phenyl-pentyl)-benzamide 

Relevant academic research and scientific papers

Asymmetric synthesis of chiral amines by highly diastereoselective 1,2- additions of organometallic reagents to N-tert-butanesulfinyl imines

High yielding and highly diastereoselective methods for 1,2-additions of organometallic reagents to N-tert-butanesulfinyl aldimines (2) and N-tert- butanesulfinyl kerimines (3) are described. The additions of alkyl, aryl, alkenyl, and allyl carbanions to a diverse set of imines with different steric and electronic properties are demonstrated. Acidic methanolysis of the sulfinamide products (4 and 6) delivers highly enantioenriched α-branched and α,α-dibranched amines. Since a broad range of sulfinyl imines are easily accessible from aldehydes and ketones, a wide variety of enantioentriched amines may be prepared.

Transition Structure Geometries for Transfers of Neutral and Anionic Nitrogen to Lithiated Carbanions

The geometries of nucleophilic substitutions at neutral and anionic nitrogen by organolithium species have been investigated. The demonstration of an intramolecular conversion of 9 to 10 provides an endocyclic restriction test which supports a trigonal bipyramidal transition structure for nitrogen transfer. A lack of isotopic scrambling of 12a-18O during nitrogen transfer is taken to rule out reaction via an oriented ion pair. Attempted endocyclic restriction tests for transfers of formally anionic nitrogen with 32 and 33 were not successful. Reactions of n-butyl, s-butyl and tert-butyllithium reagents with 16, 23, 30, 31, and 36-38 generally afford higher yields with increasing substitution at the carbon of the organolithium reagent and with decreasing substitution adjacent to the nitrogen of the aminating reagent. These results are consistent with trigonal bipyramidal transition states for nucleophilic displacements of oxygen by carbon at neutral and anionic nitrogen.

Process for the preparation of tertiary carbinamines

This invention relates to a novel process for the preparation of tertiary carbinamines by double addition of organolanthanide reagents, especially organocerium reagents, to nitriles. It further relates to the preparation of such amines by the addition of

Tertiary Carbinamines by Addition of Organocerium Reagents to Nitriles and Ketimines

Organocerium reagents, prepared by reaction of aromatic and primary and secondary alkyllithium reagents with anhydrous cerium chloride, add to nitriles twice to give tertiary carbinamines in often excellent yields.Addition of n-BuCeCl2 to acetophenone is about 4 times faster than addition to benzonitrile.Only 1,2-diaddition is observed in the reaction of MeCeCl2 with cinnamonitrile.The species formed in the double addition of organocerium reagents to nitriles are sufficiently basic to generate a benzyne intermediate by abstraction of an aromatic proton and nucleophilic enough to undergo an intramolecular Chichibabin reaction.Reaction of N-unsubstituted ketimines or their lithium salts with organocerium reagents permits the synthesis of tertiary carbinamines with three different groups on the tertiary carbon center.

Reactions of Primary Amines with Organolithium Compounds

Primary amines react under mild conditions with an excess of an organolithium compound to form imines and α-substituted primary amines.Frequently, N-alkylamines that result from the condensation of these products are also isolated.For example, reactions of PhCH2NH2 with RLi (R = n-Bu) in refluxing hexane furnish (after hydrolysis) PhCHRNH2, PhRC=O, PhRC=NCHRPh, and R2C=O.The organic group of the primary amine can be a primary, secondary, or tertiary alkyl group.A reaction scheme is proposed that has three types of steps: (1) Mono- and dilithiation of the primary ami ne by an organolithium compound (both lithiations generally at nitrogen). (2) Elimination from the mono- or dilithiated amine of lithium hydride or (when the alkyl group is tertiary) of the elements of an organolithium compound to produce an N-lithioimine. (3) Addition of an organolithium compound to the lithioimine to produce a new dilithiated amine.The scheme rationalizes both the structures of the products and the effects of reaction conditions on product composition.Reaction of benzonitrile with an excess of n-butyllithium furnishes (after hydrolysis) di-n-butyl ketone as the major product.Since this reaction must also proceed through an N-lithioimine, formation of this product provides additional evidence for the proposed addition and elimination steps.