777067-25-1Relevant articles and documents
P-stereogenic pinene-derived phosphoramidites and their use in copper-catalyzed conjugate additions
Hobuss, Dennis,Baro, Angelika,Axenov, Kirill V.,Laschat, Sabine,Frey, Wolfgang
, p. 384 - 392 (2011)
New P-stereogenic phosphoramidites based on a (-)-pinane framework were synthesized and investigated by NMR spectroscopic methods and single-crystal X-ray structural analysis. The reaction between cis-pinandiol 2 and N,N-dialkylphosphoramidous dichlorides
Enantioselective Alkoxycyclization of 1,6-Enynes with Gold(I)-Cavitands: Total Synthesis of Mafaicheenamine C
Martín-Torres, Inmaculada,Ogalla, Gala,Yang, Jin-Ming,Rinaldi, Antonia,Echavarren, Antonio M.
supporting information, p. 9339 - 9344 (2021/03/18)
Chiral gold(I)-cavitand complexes have been developed for the enantioselective alkoxycyclization of 1,6-enynes. This enantioselective cyclization has been applied for the first total synthesis of carbazole alkaloid (+)-mafaicheenamine C and its enantiomer, establishing its configuration as R. The cavity effect was also evaluated in the cycloisomerization of dienynes. A combination of experiments and theoretical studies demonstrates that the cavity of the gold(I) complexes forces the enynes to adopt constrained conformations, which results in the high observed regio- and stereoselectivities.
Concise synthesis and applications of enantiopure spirobiphenoxasilin-diol and its related chiral ligands
Liu, Tao,Wang, Biqin,Wang, Peng,Wu, Yichen,Xu, Wen-Qiang,Yang, Lei
, p. 13365 - 13368 (2021/12/17)
The development of chiral architectures for chiral ligand and catalyst discovery is essential for asymmetric catalysis. Herein, we report the concise synthesis of a Si-centered spirocyclic skeleton, spirobiphenoxasilin-diol (SPOSiOL), and its derived chiral ligands. Using the chemical resolution method, the optical SPOSiOL could be obtained in high yield on a gram scale. Preliminary studies indicated that this ligand scaffold has great potential in transition metal-catalyzed asymmetric reactions. This finding further highlights that the Si-centered spirocyclic scaffolds are of great value in asymmetric catalysis. This journal is
Asymmetric Synthesis and Application of Chiral Spirosilabiindanes
Chang, Xin,Chen, Hong-Chao,Li, Chuan-Ying,Ma, Pei-Long,Wang, Peng
supporting information, p. 8937 - 8940 (2020/04/30)
Reported here is the development of a class of chiral spirosilabiindane scaffolds by Rh-catalyzed asymmetric double hydrosilation, for the first time. Enantiopure SPSiOL (spirosilabiindane diol), a new type of chiral building block for the preparation of various chiral ligands and catalysts, was readily prepared on greater than 10 gram scale using this protocol. The potential of this new spirosilabiindane scaffold in asymmetric catalysis was preliminarily demonstrated by development of the corresponding monodentate phosphoramidite ligands (SPSiPhos), which were used in both a Rh-catalyzed hydrogenation and a Pd-catalyzed intramolecular carboamination.
Spiro-dihydrobenzo-silole diphenol compounds, synthesis method and application thereof (by machine translation)
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Paragraph 0723-0725, (2020/06/17)
The invention discloses a spirodiclole diphenol compound as shown in a formula I as well as a synthesis method and application thereof. The method has the characteristics of simplicity and convenience in operation, easily available raw materials, mild rea
Investigating the Enantiodetermining Step of a Chiral Lewis Base Catalyzed Bromocycloetherification of Privileged Alkenes
B?se, Dietrich,Denmark, Scott E.
supporting information, p. 433 - 439 (2017/11/22)
The development of catalytic, enantioselective halofunctionalizations of unactivated alkenes has made significant progress in recent years. However, the identification of generally applicable catalysts for wide range of substrates has yet to be realized.
Chiral Cyclohexyl-Fused Spirobiindanes: Practical Synthesis, Ligand Development, and Asymmetric Catalysis
Zheng, Zhiyao,Cao, Yuxi,Chong, Qinglei,Han, Zhaobin,Ding, Jiaming,Luo, Chenguang,Wang, Zheng,Zhu, Dongsheng,Zhou, Qi-Lin,Ding, Kuiling
supporting information, p. 10374 - 10381 (2018/08/03)
1,1′-Spirobiindane has been one type of privileged skeleton for chiral ligand design, and 1,1′-spirobiindane-based chiral ligands have demonstrated outstanding performance in various asymmetric catalysis. However, the access to enantiopure spirobiindane is quite tedious, which obstructs its practical application. In the present article, a facile enantioselective synthesis of cyclohexyl-fused chiral spirobiindanes has been accomplished, in high yields and excellent stereoselectivities (up to >99% ee), via a sequence of Ir-catalyzed asymmetric hydrogenation of α,α′-bis(arylidene)ketones and TiCl4 promoted asymmetric spiroannulation of the hydrogenated chiral ketones. The protocol can be performed in one pot and is readily scalable, and has been utilized in a 25 g scale asymmetric synthesis of cyclohexyl-fused spirobiindanediol (1S,2S,2′S)-5, in >99% ee and 67% overall yield for four steps without chromatographic purification. Facile derivations of (1S,2S,2′S)-5 provided straightforward access to chiral monodentate phosphoramidites 6a-c and a tridentate phosphorus-amidopyridine 11, which were evaluated as chiral ligands in several benchmark enantioselective reactions (hydrogenation, hydroacylation, and [2 + 2] reaction) catalyzed by transition metal (Rh, Au, or Ir). Preliminary results from comparative studies showcased the excellent catalytic performances of these ligands, with a competency essentially equal to the corresponding well-established privileged ligands bearing a regular spirobiindane backbone. X-ray crystallography revealed a close resemblance between the structures of the precatalysts 20 and 21 and their analogues, which ultimately help to rationalize the almost identical stereochemical outcomes of reactions catalyzed by metal complexes of spirobiindane-derived ligands with or without a fused cyclohexyl ring on the backbone. This work is expected to stimulate further applications of this type of readily accessible skeletons in development of chiral ligands and functional molecules.
Practical synthesis of simplephos ligands: Further development of alkyl-substituted phosphanamines
Mueller, Daniel,Guenee, Laure,Alexakis, Alexandre
supporting information, p. 6335 - 6343 (2013/10/21)
Herein we disclose a rapid and easy synthetic procedure to access aryl- and alkyl-substituted phosphanamines (SimplePhos ligands). During the synthesis of a library of diverse aryl-substituted phosphanamine ligands we also found that alkyl-substituted phosphanamines can be synthesized and handled easily. This was unexpected as a previous report described them as highly air-sensitive compounds. Subsequently, we created a library of alkyl-substituted phosphanamines and found some to be highly efficient ligands in copper-catalyzed reactions such as the Cu-catalyzed asymmetric conjugate addition and propargylic alkylation reactions. Moreover, our efforts towards the synthesis of SimplePhos ligands led to the development of an easy and practical synthesis of diaryl(chloro)phosphanes, which is also presented in this paper. Copyright
Highly enantioselective copper-catalyzed allylic alkylation with atropos phosphoramidites bearing a D2-symmetric biphenyl backbone
Fang, Fang,Zhang, Hui,Xie, Fang,Yang, Guoqiang,Zhang, Wanbin
experimental part, p. 3593 - 3598 (2010/06/21)
A novel class of atropos dibridged biphenyl phosphoramidites bearing a D2-symmetric biphenyl backbone was prepared and applied as chiral ligands in the copper-catalyzed allylic alkylation with Grignard reagent. The alkylation products were obtained in quantitative yields with high regioselectivities up to 94:6 of SN2′/SN2 ratio and enantiomeric excesses up to 91.1% for SN2′ products. The unique D2-symmetric backbone ligands have the advantages of easy preparation and sufficient reusability of their key intermediates from the undesired isomers.
Modular synthesis of novel chiral phosphorous triamides based on (S)-N(pyrrolidin-2-ylmethyl)aniline and their application in asymmetric catalysis
Barta, Katalin,Hoelscher, Markus,Francio, Giancarlo,Leitner, Walter
experimental part, p. 4102 - 4116 (2009/12/26)
A set of new P-chiral phosphorous triamides (PTAs) based on the (S)-N-(pyrrolidin-2-ylmethyl)aniline backbone was prepared by modular synthetic procedures. The chirality at: phosphorus can be controlled to a large extent by the synthetic route, and high d
