67705-11-7

Upstream product

• 56671-82-0 3-Iodocyclohex-2-enone 
• 42599-18-8 (E)-1-hexenyldihydroxyborane 
• 930-68-7 cyclohexenone 
• 126688-97-9 2-[(1E)-hex-1-en-1-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 5323-87-5 3-Ethoxycyclohex-2-en-1-one 
• 119245-02-2 (E)-3-hexenyl iodide 
• 693-02-7 hex-1-yne 
• 77708-66-8 3-oxocyclohex-1-en-1-yl 4-methylbenzenesulfonate 
• 56671-81-9 3-bromo-2-cyclohexen-1-one 
• 124582-25-8 (E)-tributyl(hex-1-en-1-yl)stannane 
• 75700-18-4 3-<(Methanesulfonyl)oxy>-2-cyclohexenone 
• 137097-73-5 C₁₂H₂₂Zn 

Downstream Products

• 864148-39-0 (R)-1-(3-methoxyphenyl)-2-phenylhexane 
• 864148-40-3 (R)-1-(3-hydroxyphenyl)-2-phenylhexane 
• 864148-41-4 (R)-1-(3-(trifluoromethanesulfonyloxy)phenyl)-2-phenylhexane 
• 864148-34-5 (R)-3-(2-phenylhexyl)-2-cyclohexen-1-one 

Relevant academic research and scientific papers

Suzuki-Type Cross Coupling Reactions Using Palladium-Water Soluble Catalyst. Synthesis of Functionalized Dienes.

The palladium(0) catalyzed cross-coupling of boronic acids or esters conducted with a water soluble catalyst in the presence of organic base allows under mild codition the production of functionalized dienes (60-90percent yield). - Keywords: Dienes, Trien

Enantioselective 1,6-conjugate addition to cyclic dienones catalyzed by the Cu-DiPPAM complex

Figure Presented. In the presence of a Cu/DiPPAM catalytic system, various diorganozinc reagents realize 1,6-asymmetric conjugate addition on various cyclic five- and six-membered cyclic dienones, with complete regioselectivity and high ees (93-99%).

Oxidative palladium(II) catalysis: A highly efficient and chemoselective cross-coupling method for carbon-carbon bond formation under base-free and nitrogenous-ligand conditions

We report herein the development of a general and mild protocol of oxygen-promoted Pd(II) catalysis resulting in the selective cross-couplings of alkenyl- and arylboron compounds with various olefins. Unlike most cross-coupling reactions, this new methodology works well even in the absence of bases, consequently averting undesired homo-couplings. Nitrogen-based ligands including dimethyl-phenanathroline enhance reactivities and offer a highly efficient and stereoselective methodology to overcome challenging substrate limitations. For instance, oxidative palladium(II) catalysis is effective with highly substituted alkenes and cyclic alkenes, which are known to be incompatible with other known catalytic conditions. Most examined reactions progressed smoothly to completion at low temperatures and in short times. These interesting results provide mechanistic insights and utilities for a new paradigm of palladium catalytic cycles without bases.

Rhodium-catalyzed asymmetric 1,6-addition of aryl zinc reagents to dienones

(Chemical Equation Presented) A highly enantioselective methodology allows the preparation of α,β-unsaturated ketones that contain a new stereogenic center at the C5 position. This approach is realized through the title reaction in the presence of chlorotrimethylsilane as a Lewis acid and a rhodium/(S)-binap complex as the catalyst followed by acidic hydrolysis (see scheme). binap = 2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl.

Oxygen-promoted palladium(II) catalysis: Facile C(sp2)-C(sp 2) bond formation via cross-coupling of alkenylboronic compounds and olefins

(Chemical Equation Presented) Oxygen-promoted Pd(II) catalysis facilitated the synthesis of conjugated dienes by cross-coupling of alkenylboronic compounds and various olefins including highly substituted alkenes and cyclohexenone. Under mild conditions, these versatile reactions were efficient and highly stereoselective.

STRICTLY REGIO-CONTROLLED METHOD FOR α-ALKENYLATION OF CYCLIC KETONES VIA PALLADIUM-CATALYZED CROSS COUPLING

Cyclic α-iodoenones and α-triflyloxyenones, but not α-bromoenones, smoothly react with alkenylzinc and related derivatives in the presence of a catalytic amount of a palladium-phosphine complex, such as Pd(PPh3)4 or Cl2Pd(PPh3)2 treated with n-BuLi (2 equiv), to give α-alkenylenones which can be conjugatively reduced to the corresponding α-alkenyl ketones with complete retention of both enone regiochemistry and alkenyl stereochemistry.

Palladium-Catalyzed Cross-Coupling of β-(Methanesulfonyl)oxy Enones with Organostannanes

β-(Methanesulfonyl)oxy enones, derived from 1,3-diones, cross-couple with vinylstannanes in 50-80percent yields when a substoichiometric amount of Pd(PPh3)4 and stoichiometric lithium bromide are used.Phenyltributylstannane affords low yields of cross-coupled product.Tetrabutyltin, tributyltin hydride, and ethynyltributyltin do not couple under the reaction conditions.The reaction is proposed to involve in situ formation of the β-bromo enone, oxidative addition to the Pd(0) catalyst, transmetalation, and reductive elimination to afford cross-coupled products.The analogous enol phosphates undergo coupling in low yields, the major product resulting from regeneration of the 1,3-dione.

Palladium- or Nickel-Catalyzed Reactions of Alkenylmetals with Unsaturated Organic Halides as a Selective Route to Arylated Alkenes and Conjugated Dienes: Scope, Limitations, and Mechanism

Stereo- and regiodefined alkenylmetals containing Al, Zr, and Zn react with aryl and alkenyl iodides and bromides in the presence of catalytic amounts of Pd or Ni complexes containing phosphine ligands, such as PPh3, to give the corresponding cross-coupled products.Palladium catalysts permit nearly 100 percent stereospecificity in both alkenyl-aryl and alkenyl-alkenyl coupling reactions, whereas nickel catalysts lead to partial stereochemical scrambling in the alkenyl-alkenyl coupling.Although many other metals including Li, Mg, Cd, Hg, B, Si, Sn, Ti, and Ce were also used, the results were inferior to those obtained with Al, Zr, and Zn under the conditions used in the present study.The turnover numbers for the palladium-catalyzed reactions of PhI with (E)-1-octenylmetals containing Al, Zr, and Zn were 2,3, and > 2000 mmol of (E)-1-octenylbenzene (8) per mmol of Pd(PPh3)4 per hour at room temperature, respectively.The stoichiometric reaction of PhPd(PPh3)2I (6) with 1.2 equiv of (E)-1-octenylzinc chloride (7) in a 2:1 mixture of CD2Cl2 and THF was examined in detail.The reaction follows second-order konetics (k2 = 2.9 L/(mol.min) at 0 deg C) to give 8 without the buildup of any intermediate.The results are consistent with a slow formation of 9 via transmetalation followed by its rapid reductive elmination to give 8 and "Pd(PPhe3)2".Addition of PhI to the reaction mixture rapidly gives 6 in 98 percent yield, supporting the plausibility of the proposed oxidative addition step.These results are consistent with the proposed mechanism consisting of oxidative addition of Pd(0) complexes, rate-determining transmetalation involving Pd(II) complexes, and rapid decomposition of diorganopalladium(II) species to produce the coupling products in one or more subsequent steps.The rate-determining transmetalation step provides an explanation for the effect of metals in organometallic reagents used stoichiometrically.