22039-97-0Relevant articles and documents
Evaluation of the relative magnitude of the β-effect of silicon and the γ-effect of tin by intermolecular competition
Sugawara, Masanobu,Yoshida, Jun-Ichi
, p. 1253 - 1257 (2000)
The relative magnitude of the β-effect of silicon and the γ-effect of tin was evaluated by intermolecular competition. An acetal was allowed to react with a 1:1 mixture of an allylsilane and a homoallylstannane in the presence of TMSOTf (trimethylsilyl trifluoromethanesulfonate); the former was found to be more reactive than does the latter, indicating that the β-silyl group activates the carbon-carbon double bond more effectively than the γ- stannyl group. This is consistent with the results of molecular-orbital calculations which indicate that the HOMO level of the allylsilane is higher than that of the homoallylstannane. The intermolecular competition between a homoallylstannane and a terminal alkene toward electrophilic reactions with an acetal have revealed that the former is more reactive than the latter. This result indicates that the stannyl group at the γ-position definitely activates the carbon-carbon double bond toward electrophiles.
Highly chemoselective lithium metal reductions of benzaldehyde bis(2-methoxyethyl) acetals
Von Schrader, Thomas,Woodward, Simon
, p. 3833 - 3836 (2002)
Naphthalene-catalysed reductions of PhCH(OR)2 (R = Me, CH2CH2OMe) acetals by lithium metal, followed by reactions with electrophiles (H+, TMSCl, nBuBr, CH2=CHCH2Br), proceed with high chemoselectivity when the reductions are carried out at -90 °C especially for R = CH2CH2OMe. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany 2002.
REGIOSPECIFIC ALLYLATION OF ACETALS WITH ALLYLSILANES CATALYZED BY IODOTRIMETHYLSILANE. SYNTHESIS OF HOMOALLYLETHERS
Sakurai, Hideki,Sasaki, Koshi,Hosomi, Akira
, p. 745 - 748 (1981)
Allylation of acetals with allylsilanes is catalyzed by iodotrimethylsilane to give the corresponding homoallyl ethers, with regiospecific transposition of the allyl group.
The Hosomi-Sakurai allylation in hexafluoroisopropanol: Solvent promotion effect
Panchenko, Svetlana P.,Runichina, Sofia A.,Tumanov, Vasily V.
, p. 226 - 228 (2011)
Hydrogen bond donating capacity of hexafluoroisopropanol was shown to be responsible for both the formation of its stoichiometric complexes with aldehydes and acetals and subsequent facilitation of their reactions with allylsilanes.
TRIMETHYLSILYL TRIFLUOROMETHANESULFONATE AS A CATALYST OF THE REACTION OF ALLYLTRIMETHYLSILANE AND ACETALS
Tsunoda, T.,Suzuki, M.,Noyori, R.
, p. 71 - 74 (1980)
In the presence of a catalytic amount of trimethylsilyl trifluoromethanesulfonate, allyltrimethylsilane reacts with acetals to give the corresponding homoallyl ethers in high yields.
Oxoammonium-Mediated Allylsilane–Ether Coupling Reaction
Carlet, Federica,Bertarini, Greta,Broggini, Gianluigi,Pradal, Alexandre,Poli, Giovanni
, p. 2162 - 2168 (2021/04/02)
A new C(sp3)?H functionalization reaction consisting of the oxidative α-allylation of allyl- and benzyl- methyl ethers has been developed. The C?C coupling could be carried out under mild conditions thanks to the use of cheap and green oxoammonium salts. The scope of the reaction was studied over 27 examples, considering the nature of the substituents on the two coupling partners.
Organophotoredox/palladium dual catalytic decarboxylative Csp3-Csp3coupling of carboxylic acids and π-electrophiles
Cartwright, Kaitie C.,Tunge, Jon A.
, p. 8167 - 8175 (2020/09/09)
A dual catalytic decarboxylative allylation and benzylation method for the construction of new C(sp3)-C(sp3) bonds between readily available carboxylic acids and functionally diverse carbonate electrophiles has been developed. The new process is mild, operationally simple, and has greatly improved upon the efficiency and generality of previous methodology. In addition, new insights into the reaction mechanism have been realized and provide further understanding of the harnessed reactivity.
Multicatalytic Stereoselective Synthesis of Highly Substituted Alkenes by Sequential Isomerization/Cross-Coupling Reactions
Romano, Ciro,Mazet, Clément
supporting information, p. 4743 - 4750 (2018/04/10)
Starting from readily available alkenyl methyl ethers, the stereoselective preparation of highly substituted alkenes by two complementary multicatalytic sequential isomerization/cross-coupling sequences is described. Both elementary steps of these sequences are challenging processes when considered independently. A cationic iridium catalyst was identified for the stereoselective isomerization of allyl methyl ethers and was found to be compatible with a nickel catalyst for the subsequent cross-coupling of the in situ generated methyl vinyl ethers with various Grignard reagents. The method is compatible with sensitive functional groups and a multitude of olefinic substitution patterns to deliver products with high control of the newly generated C=C bond. A highly enantioselective variant of this [Ir/Ni] sequence has been established using a chiral iridium precatalyst. A complementary [Pd/Ni] catalytic sequence has been optimized for alkenyl methyl ethers with a remote C=C bond. The final alkenes were isolated with a lower level of stereocontrol. Upon proper choice of the Grignard reagent, we demonstrated that C(sp2) - C(sp2) and C(sp2) - C(sp3) bonds can be constructed with both systems delivering products that would be difficult to access by conventional methods.
Catalytic Use of Elemental Gallium for Carbon-Carbon Bond Formation
Qin, Bo,Schneider, Uwe
supporting information, p. 13119 - 13122 (2016/10/25)
The first catalytic use of Ga(0) in organic synthesis has been developed by using a Ag(I) cocatalyst, crownether ligation, and ultrasonic activation. Ga(I)-catalyzed C-C bond formations between allyl or allenyl boronic esters and acetals, ketals, or aminals have proceeded in high yields with essentially complete regio- and chemoselectivity. NMR spectroscopic analyses have revealed novel transient Ga(I) catalytic species, formed in situ through partial oxidation of Ga(0) and B-Ga transmetalation, respectively. The possibility of asymmetric Ga(I) catalysis has been demonstrated.
Highly efficient triphenyl(3-sulfopropyl)phosphonium functionalized phosphotungstic acid on silica as a solid acid catalyst for selective mono-allylation of acetals
Kamble, Sumit B.,Shinde, Suhas H.,Rode, Chandrashekhar V.
, p. 4039 - 4047 (2015/08/03)
Silica supported phosphotungstic acid functionalized with triphenyl(3-sulfopropyl)phosphonium (PW-Si/TPSP) was developed as a solid acid catalyst for C-C bond formation via Hosomi-Sakurai allylation of acetals. Functionalization of PW as well as its bindi
