13197-81-4

Upstream product

• 1184-58-3 dimethylaluminum chloride 
• 591-51-5 phenyllithium 
• 108-86-1 bromobenzene 
• 100-58-3 phenylmagnesium bromide 
• 75-24-1 trimethylaluminum 
• 100-59-4 phenylmagnesium chloride 

Downstream Products

• 53750-06-4 (R)-methyl 3-oxo-1-phenylcyclopentanecarboxylate 
• 131726-64-2 (S)-methyl 3-oxo-1-phenylcyclopentanecarboxylate 
• 898253-17-3 (S)-3-methyl-3-phenylcyclohexan-1-one 
• 1200657-22-2 (1R,2S)-2-phenyl-1,2-dihydronaphthalen-1-ol 
• 1169869-80-0 (1S,2R)-2-phenyl-1,2-dihydronaphthalen-1-ol 
• 457625-20-6 (1S,2R)-(-)-2-methyl-1,2-dihydronaphth-1-ol 
• 905832-87-3 (R)-3-methyl-3-phenylcyclohexan-1-one 
• 1235989-02-2 (S)-4,8-dimethyl-4-phenylnon-7-en-2-one 
• 1092571-63-5 (R)-3-ethyl-3-phenylcyclohexanone 
• 1092571-65-7 (R)-3-phenyl-3-methylcycloheptanone 
• 1092571-64-6 (R)-3-phenyl-3-isobutylcyclohexanone 
• 1189241-02-8 (S)-4-methyl-4,6-diphenylhexan-2-one 
• 1189241-03-9 (R)-4-methyl-4,6-diphenylhexan-2-one 
• 1610853-55-8 (S)-N-(1-phenylcyclohex-2-en-1-yl)-4-methylbenzenesulfonamide 

Relevant academic research and scientific papers

Aluminium-Catalyzed C(sp)?H Borylation of Alkynes

Historically used in stoichiometric hydroalumination chemistry, recent advances have transformed aluminium hydrides into versatile catalysts for the hydroboration of unsaturated multiple bonds. This catalytic ability is founded on the defining reactivity of aluminium hydrides with alkynes and alkenes: 1,2-hydroalumination of the unsaturated π-system. This manuscript reports the aluminium hydride catalyzed dehydroborylation of terminal alkynes. A tethered intramolecular amine ligand controls reactivity at the aluminium hydride centre, switching off hydroalumination and instead enabling selective reactions at the alkyne C?H σ-bond. Chemoselective C?H borylation was observed across a series of aryl- and alkyl-substituted alkynes (21 examples). On the basis of kinetic and density functional theory studies, a mechanism in which C?H borylation proceeds by σ-bond metathesis between pinacolborane (HBpin) and alkynyl aluminium intermediates is proposed.

Cobalt-catalyzed cross-coupling reactions of aryl- And alkylaluminum derivatives with (hetero)aryl and alkyl bromides

A simple cobalt complex, such as Co(phen)Cl2, turned out to be a highly efficient and cheap precatalyst for a host of cross-coupling reactions involving aromatic and aliphatic organoaluminum reagents with aryl, heteroaryl and alkyl bromides. New C(sp2)-C(sp2) and C(sp2)-C(sp3) bonds were formed in good to excellent yields and with high chemoselectivity, under mild reaction conditions.

Nickel-Catalyzed Allylmethylation of Alkynes with Allylic Alcohols and AlMe3: Facile Access to Skipped Dienes and Trienes

We present herein an unprecedented allylative dicarbofunctionalization of alkynes with allylic alcohols. This simple catalytic procedure utilizes commercially available Ni(COD)2, triphenylphosphine, and inexpensive reagents, and delivers valuable skipped dienes and trienes with an all-carbon tetrasubstituted alkene unit in a highly stereoselective fashion. Preliminary mechanistic studies support the reaction pathway of allylnickelation followed by transmetalation in this dicarbofunctionalization of alkynes.

A study on Zr-Ir multiple bonding active for C-H bond cleavage

Zr-Ir hydrido complexes with ansa-(cyclopentadienyl)(amide) as the supporting ligand in the zirconium fragment, e.g., (L1ZrR) (Cp*Ir)(μ-H)3 [L1 = Me2Si(η 5-C5Me4)(NtBu), R = Cl (5), Ph (7), Me (10), alkyl, and aryl] were designed, synthesized, and isolated as tractable early-late heterodinuclear complexes. Despite the presence of the three supporting hydride ligands, Zr-Ir distances in the crystal structures of 5, alkyl, and aryl complexes [2.74-2.76 A] were slightly longer than the sum of the element radii of Zr and Ir [2.719 A]. These hydrocarbyl complexes displayed the thermolytic C-H activation of a variety of aromatic compounds and several organometallic compounds. Also, the substrate scope and limitation in the Zr-Ir system were studied. The regiochemical outcomes during the C-H activation of pyridine derivatives and methoxyarenes suggested the in situ generation of a Lewis acidic active intermediate, i.e., (L1Zr) (Cp*IrH2) (III). The existence of III and relevant σ-complex intermediates {L1Zr(η2-R-H)} (Cp*IrH2) (IIR) (R = Me, Ph) in the ligand exchange was demonstrated by the direct isolation of a Et3PO-adduct of III (39b) from 7 and kinetic studies. The structure of the direct Zr-Ir bonds in IIPh, IIMe, III, and 39b were probed using computational studies. The unprecedented strong M-M′ interactions in the early-late heterobimetallic (ELHB) complexes have been proposed herein.

Rhodium-catalyzed enantioselective addition of organoaluminum reagents to N -tosyl ketimines

Rhodium(I)/Binap complexes catalyze highly enantioselective additions of methyl- and arylaluminum reagents to cyclic α,β-unsaturated N-tosyl ketimines. Depending on the solvent and substituents at the ring, the reaction occurs either in a 1,2-manner to de

Catalytic enantioselective protoboration of disubstituted allenes. Access to alkenylboron compounds in high enantiomeric purity

Proto-boryl additions to 1,1-disubstituted allenes in the presence of 1.0-5.0 mol % of chiral NHC-Cu complexes, B2(pin)2, and t-BuOH proceed to afford alkenyl-B(pin) products in up to 98% yield, >98:2 site selectivity, and 98:2 er. T

Copper-catalyzed asymmetric conjugate addition of alkenyl- and alkylalanes to α,β-unsaturated lactams

Alkenyl and alkyl groups have been successfully introduced to six-membered α,β-unsaturated lactams via a copper-catalyzed asymmetric 1,4-addition of the corresponding alanes. Moderate to good yields and good to excellent enantioselectivities are achieved by using a combination of the very cheap copper(II) naphthenate and a readily available phosphine amine ligand. The creation of an all-carbon quaternary stereogenic center, via Michael addition to a trisubstituted conjugated lactam, is also disclosed for the first time.

Enantioselective synthesis of quaternary carbon stereogenic centers through copper-catalyzed conjugate additions of aryl- and alkylaluminum reagents to acyclic trisubstituted enones

Acyclic quaternary carbons by conjugate addition: The first examples of catalytic enantioselective conjugate additions of aryl and alkyl units that generate acyclic all-carbon quaternary stereogenic centers have been developed (see scheme). The requisite

Enantioselective synthesis of all-carbon quaternary stereogenic centers by catalytic asymmetric conjugate additions of alkyl and aryl aluminum reagents to five-, six-, and seven-membered-ring β-substituted cyclic enones

(Chemical Equation Presented) Solution to pesky problems: Effective methods for catalytic asymmetric conjugate additions of alkyl and aryl aluminum reagents with unactivated β-substituted cyclopentenones are now available (see scheme). Transformations, pr

1,5-Asymmetric induction of chirality: Diastereoselective addition of organoaluminium reagents and allylstannanes into aldehyde groups in the side-chain of π-allyltricarbonyliron lactone complexes

π-Allyltricarbonyliron lactone complex 5, bearing an aldehyde group in the side-chain, can be easily prepared from commercially available (2E,4E)-ethyl hexadienoate and reacts with organoaluminium and allylstannane nucleophiles to afford secondary alcohols. In analogy with the corresponding ketone-substituted complexes, the lactone tether acts via the Fe(CO)3 moiety as a source of asymmetric induction. The levels of diastereoselectivity are generally reduced, however, compared with those obtained using ketone complexes. This can be attributed, at least in part, to the carbonyl appendage adopting both s-cis and s-trans conformations. The level of 1,5-asymmetric induction is strongly dependent upon the nature of the nucleophile in the case of the organoaluminium reactions and upon the reaction temperature in the case of BF3-mediated addition of allylstannanes into the aldehyde group.