- Reductive Difunctionalization of Aryl Alkenes with Sodium Metal and Reduction-Resistant Alkoxy-Substituted Electrophiles
-
A general method for alkali-metal-promoted reductive difunctionalization of alkenes has been developed by means of reduction-resistant alkoxy-substituted electrophiles. A series of 1,2-diboration and 1,2-dicarbofunctionalization products can be synthesize
- Fukazawa, Mizuki,Nogi, Keisuke,Sasamori, Takahiro,Takahashi, Fumiya,Yorimitsu, Hideki
-
supporting information
(2020/03/13)
-
- New C2-symmetrical 1,2-diphosphanes for the efficient rhodium-catalyzed asymmetric hydroboration of styrene derivatives
-
A double [2,3] sigmatropic rearrangement enables the fast synthesis of novel C2-symmetrical 1,2-diphosphanes in good yields. These phosphanes (for example, 1; c-Hex = cyclohexyl) are highly efficient ligands for the rhodium-catalyzed asymmetric hydroboration of a wide variety of styrenes (see scheme). cod = 1,5-cyclooctadiene; DME = 1,2-dimethoxyethane.
- Demay, Steandphane,Volant, Florence,Knochel, Paul
-
p. 1235 - 1238
(2007/10/03)
-
- Enantioselective preparation of a novel chiral 1,2-diamine
-
A short enantioselective preparation of (1S,2S)-trans-1,2-diamino-3-cyclohexene using a double [3,3]-sigmatropic rearrangement of an allylic bis(imidate) is described (Overman rearrangement). The starting chiral diol is conveniently obtained by enzymatic resolution.
- Demay, Stéphane,Kotschy, Andras,Knochel, Paul
-
p. 863 - 866
(2007/10/03)
-
- Synthetic applications of functionalized silyl anions: Aminosilyl anions as hydroxy anion equivalent
-
An (aminosilyl)lithium and the corresponding copper and magnesium reagents serve as a hydroxy anion equivalent through (1) allylic substitution, (2) addition to vinyloxirane, and (3) addition to acetylene, followed by oxidative cleavage of the silicon-carbon bonds. Highly regio- and stereoselective transformations have been achieved in all cases.
- Tamao, Kohei,Kawachi, Atsushi,Tanaka, Yoko,Ohtani, Hitoshi,Ito, Yoshihiko
-
p. 5765 - 5772
(2007/10/03)
-
- SYNTHESIS OF A SIMPLE MODEL OF THE CARCINOGENIC EPOXYDIOLS AND INVESTIGATION OF ITS MUTAGENIC ACTIVITY
-
Whereas epoxidation of trans-3-cyclohexene-1,2-diol with MCPBA is highly stereospecific, yielding the anti and syn epoxides in a ratio of 98:2, the corresponding dibenzoate gives the anti-epoxide in low yield, since the more reactive syn-epoxide decompose
- Berti, Giancarlo,Mastrorilli, Ettore,Bronzetti, Giorgio
-
p. 449 - 452
(2007/10/02)
-
- Vinyl Epoxide Hydrolysis Reactions
-
The rates of hydrolysis of cyclopentadiene oxide (3), cyclohexadiene oxide (4), cycloheptadiene oxide (5), cyclooctadiene oxide (6), butadiene oxide (7), and styrene oxide (8) have been determined as a function of pH.Each epoxide exhibited acid-catalyzed hydrolysis at low pH, and 3-5 showed significant rates for "spontaneous" reaction with solvent at intermediate pH values.The hydrolyses of several of the vinyl epoxides (4 and 5) showed kinetic terms in HO- at pH > ca. 13.Specific chloride effects attributed to nucleophilic addition of Cl- to neutral epoxide were observed for those compounds (3, 4, and 8) hydrolyzed in KCl solutions.From kinetic and product studies, mechanisms for hydrolyses of the vinyl epoxides are postulated.Acid-catalyzed hydrolyses of 3, 4, 5, and 6 were found to be A-1 in nature, proceeding via intermediate allyl cations.Product distributions depended on the structure of the cation.Mechanisms and product distributions for the spontaneous hydrolyses of vinyl epoxides were found to be variable, and dependent on the structure of the epoxide.
- Ross, Angela M.,Pohl, Terese M.,Piazza, Kathryn,Thomas, Michael,Fox, Bonnie,Whalen, Dale L.
-
p. 1658 - 1665
(2007/10/02)
-