185999-07-9Relevant academic research and scientific papers
Total Synthesis of (+)-Cornexistin
Barber, David M.,Magauer, Thomas,Steinborn, Christian,Wildermuth, Raphael E.
supporting information, p. 17282 - 17285 (2020/08/21)
Herein, we describe the first total synthesis of (+)-cornexistin as well as its 8-epi-isomer starting from malic acid. The robust and scalable route features a Nozaki–Hiyama–Kishi reaction, an auxiliary-controlled syn-Evans-aldol reaction, and a highly efficient intramolecular alkylation to form the nine-membered carbocycle. The delicate maleic anhydride moiety of the nonadride skeleton was constructed from a β-keto nitrile. The developed route enabled the synthesis of 165 mg (+)-cornexistin.
Diastereoselective Synthesis of Highly Substituted Tetrahydrofurans by Pd-Catalyzed Tandem Oxidative Cyclization-Redox Relay Reactions Controlled by Intramolecular Hydrogen Bonding
Brooks, Joshua L.,Xu, Liping,Wiest, Olaf,Tan, Derek S.
supporting information, p. 57 - 75 (2017/04/26)
Palladium-catalyzed oxidative cyclization of alkenols provides a convenient entry into cyclic ethers but typically proceeds with little or no diastereoselectivity for cyclization of trisubstituted olefins to form tetrahydrofurans due to the similar energi
Copper-Catalyzed Oxyboration of Unactivated Alkenes
Itoh, Taisuke,Matsueda, Takumi,Shimizu, Yohei,Kanai, Motomu
, p. 15955 - 15959 (2015/11/03)
The first regiodivergent oxyboration of unactivated terminal alkenes is reported, using copper alkoxide as a catalyst, bis(pinacolato)diboron [(Bpin)2] as a boron source, and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) as an oxygen source. The reaction is compatible with various functional groups. Two regioisomers are selectively produced by selecting the appropriate ligands on copper. The products may be used as a linchpin precursor for various other functionalizations, and net processes such as carbooxygenation, aminooxygenation, and dioxygenation of alkenes can be achieved after C-B bond transformations. Mechanistic studies indicate that the reaction involves the following steps: 1)Transmetalation between CuOtBu and (Bpin)2 to generate a borylcopper species; 2)regiodivergent borylcupration of alkenes; 3) oxidation of the thus-generated C-Cu bond to give an alkyl radical; 4)trapping of the resulting alkyl radical by TEMPO.
Stereoselective synthesis of conjugated trienols from allylic alcohols and 1-iodo-1,3-dienes
Brandt, Damien,Bellosta, Veronique,Cossy, Janine
supporting information, p. 5594 - 5597,4 (2012/12/12)
The stereoselective synthesis of conjugated trienes has been achieved from allylic alcohols and 1-iodo-1,3-dienes using Pd(OAc)2/AgOAc.
Lewis acid-promoted addition of 1,3-bis(silyl)propenes to aldehydes: A route to 1,3-dienes
Borg, Tessie,Tuzina, Pavel,Somfai, Peter
experimental part, p. 8070 - 8075 (2011/11/28)
The Lewis acid-promoted addition of 1,3-bis(silyl)-propenes to aldehydes to provide the corresponding (E)-1,3-dienes in excellent stereoselectivity and good to excellent yields is reported. The procedure is mild, base-free, and operationally straightforward.
Total synthesis of (-)-exiguolide
Cook, Cyril,Guinchara, Xavier,Liron, Frederic,Roulland, Emmanuel
supporting information; experimental part, p. 744 - 747 (2011/03/17)
The first total synthesis of the naturally occurring enantiomer of exiguolide ((-)-1) has been completed. This very convergent synthesis features the following as main steps: (I) a Trost's ruthenium-catalyzed ene-yne cross-coupling reaction (this complex transformation allows the challenging control of the C5-C28 double bond geometry along with the stereoselective construction of the tetrahydropyran ring A) and (II) a very efficient one-pot, two-step stereoselective conjugated allyllc alcohol substitution that allowed the control of the C15 stereogenic center.
Synthesis of complex allylic esters via C-H oxidation vs C-C Bond formation
Vermeulen, Nicolaas A.,Delcamp, Jared H.,White, M. Christina
supporting information; scheme or table, p. 11323 - 11328 (2010/10/04)
A highly general, predictably selective C-H oxidation method for the direct, catalytic synthesis of complex allylic esters is introduced. This Pd(II)/sulfoxide-catalyzed method allows a wide range of complex aryl and alkyl carboxylic acids to couple directly with terminal olefins to furnish (E)-allylic esters in synthetically useful yields and selectivities (16 examples, E/Z ≤ 10:1) and without the use of stoichiometric coupling reagents or unstable intermediates. Strategic advantages of constructing allylic esters via C-H oxidation vs C-C bond-forming methods are evaluated and discussed in four case studies.
Copper-catalyzed asymmetric allylic alkylation of halocrotonates: Efficient synthesis of versatile chiral multifunctional building blocks
Den Hartog, Tim,Macia, Beatriz,Minnaard, Adriaan J.,Feringa, Ben L.
experimental part, p. 999 - 1013 (2010/08/07)
The highly enantioselective synthesis of amethyl-substituted esters is reported in up to 90% yield and up to 99% ee using copper-TaniaPhos as chiral catalyst. The transformation proved scalable to at least 6.6 mmol (1.7 g scale). The products of this transformation have been further elaborated to multifunctional building blocks with a single (branched esters and acids) or multiple stereogenic centers (vicinal dimethyl esters, as well as, hydroxy- or iodosubstituted lactones).
Total synthesis of (-)-spongidepsin
Ferrie, Laurent,Reymond, Sebastien,Capdevielle, Patrice,Cossy, Janine
, p. 3441 - 3443 (2007/10/03)
A convergent and rapid stereoselective synthesis of (-)-spongidepsin has been achieved from the Roche ester in 14 steps with an overall yield of 13%.
Novel oxepane formation by TiCl4-catalyzed nucleophilic cleavage of 1- alkoxymethyl-6,8-dioxabicyclo[3.2.1]octanes
Fujiwara, Kenshu,Amano, Arika,Tokiwano, Tetsuo,Murai, Akio
, p. 1065 - 1080 (2007/10/03)
Introduction of an alkoxymethyl group at the C1 position in the 6,8- dioxabicyclo[3.2.1]octane system enabled novel formation of oxepane compounds in TiCl-4-catalyzed acetal cleavage reactions. (C) 2000 Elsevier Science Ltd.
