53188-79-7

Upstream product

• 98-53-3 4-tercbutyl-cyclohexanone 
• 79950-20-2 ZrC₄H₉(OC₄H₉)3 
• 109-65-9 1-bromo-butane 
• 109-69-3 n-Butyl chloride 
• 94616-73-6 n-butylcerium dichloride 
• 693-03-8 n-butyl magnesium bromide 
• 542-69-8 1-iodo-butane 
• 693-04-9 butyl magnesium bromide 
• 109-72-8 n-butyllithium 
• 125950-76-7 ((trimethylsilyl)oxy)(4-tert-butylcyclohexyl)trimethylstannane 

Downstream Products

• 62702-03-8 1-n-butyl-4-tert-butyl-1-cyclohexene 
• 1604828-94-5 C₁₄H₂₈O₂ 

Relevant academic research and scientific papers

Amberlyst-15: A reusable heterogeneous catalyst for the dehydration of tertiary alcohols

Tertiary alcohols react under mild conditions in the presence of Amberlyst-15 (dry) (solid-supported sulfonic acid) to give predominantly the most stable alkene in very good yield. The dehydration of tertiary alcohol functionality occurs without observation of rearrangement and polymerization products, and with outstanding substrate tolerance, which include the NHCBz, NHBoc, OSEM, OTBDMS, OBOM and ethylene ketal functional groups. Amberlyst-15 (dry) can be easily recovered from the reaction medium and reused for five cycles, maintaining the catalytic efficiency. In addition, the dehydration can occur under continuous operation.

Ligand effects on diastereoselective addition of organocerium reagents to aldehydes and cyclic ketones

A new class of chiral dialkoxy- and diaryloxyorganocerium reagent has been prepared and the diastereoselectivity of carbonyl addition reactions has been compared with that of conventional organocerium reagents.

Unprecedented Stereoselectivity in the Addition of Organoiron(II) Reagents to Cyclohaxanone Derivatives

Various organoiron(II) reagents undergo Grignard-type additions to substituted cyclohexanone derivatives, C-C bond formation occurring stereoselectively from the equatorial direction (97 - 100percent selectivity).

Ligand effects in selective carbonyl addition reactions of organomanganese and cerium reagents

Transmetalation of organolithium reagents RLi (R = CH3, n-Bu) with manganese pivalate produces reagents of the type RMnOC(O)tBu which react stereoselectively with substituted cyclohexanones to afford the axial alcohols preferentially. These rea

Synthetic utility and mechanistic studies of the aliphatic reverse brook rearrangement

The aliphatic reverse Brook rearrangement has been examined in detail. Transmetalation of [α-[(trialkylsilyl)-oxy]alkyl]trialkylstannanes occurs via a complex equilibrium favoring the most stable carbanion. The aliphatic reverse Brook rearrangement is driven forward by the rapid migration of silicon from O to C in a transient α-silyloxy carbanion due to the formation of the more stable lithium alkoxide. Cross-over experiments have shown that the rearrangement is an intramolecular process while incorporation of a radical trap revealed that the rearrangement does not involve radical intermediates. Studies of configurationally fixed stannanes derived from 4-tert-butylcyclohexanone concluded that the rearrangement occurs with retention of configuration. Preparation and reverse Brook rearrangement of optically active (S)-[α-[(trimethylsilyl)oxy]-hexyl]tributylstannane (98% ee) provided 1-(trimethylsilyl)hexanol in 97% ee. The synthetic utility of this method for the preparation of a variety of (α-hydroxyalkyl)trialkylsilanes from aldehydes has also been demonstrated.

Reactions of Carbonyl Compounds with Grignard Reagents in the Presence of Cerium Chloride

The addition of Grignard reagents to ketones is significantly enhanced by cerium chloride with remarkable supression of side reactions, particularly enolization.Some esters, which are prone to side reactions, also react readily with Grignard reagents in the presence of cerium chloride to give normal reaction products in reasonable to high yields.

Amphiphilic Reactions by Means of Exceptionally Bulky Organoaluminum Reagents. Rational Approach for Obtaining Unusual Equatorial, Anti-Cram, and 1,4 Selectivity in Carbonyl Alkylation

Exceptionally bulky, oxygenophilic organoaluminum reagents, methylaluminum bis(2,6-di-tert-4-alkylphenoxide) (MAD and MAT), have been successfully utilized for stereoselective activation of carbonyl moiety.Combination of MAD or MAT with carbon nucleophiles such as organolithiums or Grignard reagents generates a new amphiphilic reaction system in which the alkylation may be interpreted as the nucleophilic addition of a reactive organometallic compound to an electrophilically activated carbonyl substrate in order to account for the regio- and stereochemical consequences.In contrast to the ordinary alkylations, the amphilic alkylation disclosed herein would be categorized into the new, yet unexplored class of alkylation that exhibits high chemoselectivity to carbonyl compounds, and more significantly it allows excellent equatorial and anti-Cram selectivity in carbonyl alkylations, hitherto difficult by the existing methodologies.Further, unusual conjugate addition of organolithium reagents to α,β-unsaturated carbonyl compounds has been accomplished by using the amphiphilic reaction system.

The evaluation of dicyclopentadienylsamarium as a reagent in organic synthesis

SmCp2, which is easily prepared from SmI2, has been screened as a reducing agent for organic chemistry. In particular, SmCp2 promotes the pseudo-Barbier reaction between carbonyl compounds (aldehydes and ketones) and aliphatic or allylic halides more efficiently than does SmI2.

Carbon-Carbon Bond-Forming Reactions Using Cerium Metal or Organocerium(III) Reagents

Carbon-carbon bond-forming reactions using cerium metal or organocerium(III) reagents have been investigated.Cerium amalgam is an effective reagent for the chemoselective preparation of homoallylic alcohols from allyl halides and carbonyl compounds.These same reagent can also be satisfactorily employed for the Reformatsky-type reaction of α-halo esters with carbonyl compounds.It has been shown that organocerium(III) reagents are conveniently generated by the reaction of organolithiums with cerium(III)iodide or cerium(III)chloride.The reagents are less basic thanorganolithiums or Grignard reagents, and they react cleanly at -78 to -65 deg C with various carbonyl compounds to afford the addition products in high yields, even though the substrates are susceptible to enolization or metal-halogen exchange with simple organolithiums.The same reagents react also with α,β-unsaturated compounds to yield 1,2-addition products in high selectivity.