30358-99-7Relevant academic research and scientific papers
Prins cyclizations in silyl additives with suppression of epimerization: Versatile tool in the synthesis of the tetrahydropyran backbone of natural products
Chan, Kok-Ping,Loh, Teck-Peng
, p. 4491 - 4494 (2005)
(Chemical Equation Presented) A catalytic Prins cyclization reaction has been developed. The involvement of trimethylsilyl halides offers a versatile route to the formation of cis-4-halo-2,6-disubstituted tetrahydropyran rings. The problem of epimerizatio
Biocatalysts from Biosynthetic Pathways: Enabling Stereoselective, Enzymatic Cycloether Formation on a Gram Scale
Berkhan, Gesche,Geise, Hendrik,Hahn, Frank,Hollmann, Tim,Kolb, Simon,Sung, Kwang Hoon,Wagner, Lisa
, p. 4973 - 4982 (2020)
Biosynthetic pathways of natural products contain many enzymes that contribute to the rapid assembly of molecular complexity. Enzymes that form complex structural elements with multiple stereocenters, like chiral saturated oxygen heterocycles (CSOH), are
Site- And enantiodifferentiating C(sp3)-H oxidation enables asymmetric access to structurally and stereochemically diverse saturated cyclic ethers
Liu, Lei,Sun, Shutao,Yang, Yiying,Zhang, Dongju,Zhao, Ran
supporting information, p. 19346 - 19353 (2020/12/01)
A manganese-catalyzed site- and enantiodifferentiating oxidation of C(sp3)-H bonds in saturated cyclic ethers has been described. The mild and practical method is applicable to a range of tetrahydrofurans, tetrahydropyrans, and medium-sized cyclic ethers with multiple stereocenters and diverse substituent patterns in high efficiency with extremely efficient site- and enantiodiscrimination. Late-stage application in complex biological active molecules was further demonstrated. Mechanistic studies by combined experiments and computations elucidated the reaction mechanism and origins of stereoselectivity. The ability to employ ether substrates as the limiting reagent, together with a broad substrate scope, and a high level of chiral recognition, represent a valuable demonstration of the utility of asymmetric C(sp3)-H oxidation in complex molecule synthesis.
Rhodium-Catalyzed Cyclization of Terminal and Internal Allenols: An Atom Economic and Highly Stereoselective Access Towards Tetrahydropyrans
Breit, Bernhard,Schmidt, Johannes P.
supporting information, p. 23485 - 23490 (2020/10/29)
A comprehensive study of a diastereoselective Rh-catalyzed cyclization of terminal and internal allenols is reported. The methodology allows the atom economic and highly syn-selective access to synthetically important 2,4-disubstituted and 2,4,6-trisubstituted tetrahydropyrans (THP). Furthermore, its utility and versatility are demonstrated by a great functional-group compatibility and the enantioselective total synthesis of (?)-centrolobine.
Lipase-catalyzed resolution of 1-[4-(benzyloxy)phenyl]hex-5-en-3-ol: Synthesis of (-)-centrolobine
Tadiparthi, Krishnaji,Raghavendra,Kamal, Ahmed
, p. 2321 - 2326 (2017/10/06)
A practical and efficient method for the preparation of homoallylic alcohol and its successful enzymatic resolution has been developed. This lipase-catalyzed resolution process has been optimized with respect to different lipases and solvents. Moreover, M
Catalytic asymmetric intra- and intermolecular haloetherification of enones: An efficient approach to (?)-Centrolobine
Zhou, Pengfei,Cai, Yunfei,Zhong, Xia,Luo, Weiwei,Kang, Tengfei,Li, Jun,Liu, Xiaohua,Lin, Lili,Feng, Xiaoming
, p. 7778 - 7783 (2018/05/23)
A catalytic asymmetric intra- and intermolecular haloetherification of electron-deficient alkenes (halogen = Cl, Br, I) has been realized by the use of chiral metal complexes of N,N′-dioxides. In the presence of a chiral Fe(III) complex, a series of tetrahydropyran derivatives were obtained in good yields (up to 99% yield) with a high level of enantioselectivities (up to 97% ee). Promoted by a chiral Ce(III) complex, chiral oxepane derivatives could be given in good results. Moreover, the intermolecular haloetherification of chalcones catalyzed by Sc(III) complex using MeOH as nucleophile is demonstrated. This methodology also can be successfully applied to the synthesis of (?)-Centrolobine. Meanwhile, a reasonable reaction mechanism was proposed.
Stereoselective construction of 2,6- cis -disubstituted tetrahydropyrans via intramolecular amide enolate alkylation: Total synthesis of (-)-centrolobine
Latif, Muhammad,Yun, Jeong In,Seshadri, Kalapati,Kim, Hyoung Rae,Park, Chi Hoon,Park, Haeil,Kim, Hyoungsu,Lee, Jongkook
, p. 3315 - 3320 (2015/03/30)
A highly stereoselective construction of 2,6-cis-disubstituted tetrahydropyrans was achieved by using an intramolecular amide enolate alkylation with KHMDS. The efficiency and practicality of this methodology was successfully demonstrated in the total syn
Chemoenzymatic total synthesis of four stereoisomers of centrolobine
Nagarjuna, Bollipalli,Thirupathi, Barla,Venkata Rao, Chunduri,Mohapatra, Debendra K.
, p. 4916 - 4918 (2015/07/28)
Abstract Four stereoisomers of centrolobine, (3R,7S)-(-)-centrolobine (1), (3S,7S)-(-)-epi-centrolobine (2), (3S,7R)-(+)-centrolobine (3), and (3R,7R)-(+)-epi-centrolobine (4) have been achieved in an efficient manner in 24-28% overall yield over 9-10 linear steps starting from cheap and commercially available 4-methoxybenzaldehyde following chemoenzymatic protocol. The key features of this synthetic protocol are enzymatic resolution, cross-metathesis (CM), and our own developed tandem isomerization followed by C-O and C-C bond formation reaction.
Stereoselective synthesis of (-)-centrolobine
Yang, Zunhua,Kim, Hee-Doo
, p. 305 - 309 (2014/04/03)
The stereoselective synthesis of (-)-centrolobine has been accomplished starting from d-glyceraldehyde acetonide by a combination of chelation-controlled diastereoselective alkylation and ring-closing metathesis. A high degree of 1,3-asymmetric induction has been realized in an ether system.
Enantioselective synthesis of 2,6-cis-disubstituted tetrahydropyrans via a tandem catalytic asymmetric hydrogenation/oxa-Michael cyclization: An efficient approach to (-)-centrolobine
Xie, Jian-Hua,Guo, Lu-Chuan,Yang, Xiao-Hui,Wang, Li-Xin,Zhou, Qi-Lin
supporting information, p. 4758 - 4761,4 (2012/12/13)
A highly efficient one-pot process via a tandem reaction of catalytic asymmetric hydrogenation and oxa-Michael cyclization for the synthesis of 2,6-cis-disubstituted tetrahydropyrans has been developed (ee up to 99.9%, cis/trans-selectivity up to 99:1). T
