Enantioselective Access to Chiral Cyclic Sulfamidates Through Iridium‐Catalyzed Asymmetric Hydrogenation

Liu, Yuanhua; Huang, Yi-Chung; Yi, Zhiyuan; Liu, Gongyi; Dong, Xiu‐Qin; Zhang, Xumu

doi:10.1002/adsc.201801566

Cited by 16 publications

(8 citation statements)

References 69 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For example, ring-opening reactions of chiral cyclic sulfamidates can offer convenient and efficient access to chiral amines, amino alcohols, amino acids, and their derivatives (Boulton et al., 1999, Wei and Lubell, 2000, Espino et al., 2001, Cohen and Halcomb, 2001, Cohen and Halcomb, 2002, Atfani et al., 2001, Nicolaou et al., 2002, Meléndez and Lubell, 2003, Ni et al., 2007, Rönnholm et al., 2007, Baig et al., 2010, Baig et al., 2011, Venkateswarlu et al., 2014, Albu et al., 2016, Su et al., 2016, Chen et al., 2014, Kong et al., 2015, Liu et al., 2017, Wu et al., 2018). So far the asymmetric catalytic synthetic methods of chiral cyclic sulfamidates were mainly focused on transition metal-catalyzed asymmetric intramolecular amidation of sulfamate esters (Liang et al., 2002, Liang et al., 2004, Fruit and Mueller, 2004, Zhang et al., 2005, Zalatan and Du Bois, 2008, Lin et al., 2008, Ichinose et al., 2011), additions of organoboron reagents to cyclic imines (Chen et al., 2014, Chen et al., 2018, Kong et al., 2015, Liu et al., 2017, Wu et al., 2018, Nishimura et al., 2012, Nishimura et al., 2013, Luo et al., 2012a, Luo et al., 2012b, Wang et al., 2013, Hepburn et al., 2013, Wang and Xu, 2013, Zhang et al., 2016a), and asymmetric reduction of cyclic ketimines (Wang et al., 2008, Yu et al., 2009, Kang et al., 2010, Lee et al., 2011, Lee et al., 2012, Han et al., 2011, Liu et al., 2019, Itsuno et al., 2014, Seo et al., 2015, Kim et al., 2018).…”

Section: Introductionmentioning

confidence: 99%

Nickel-Catalyzed Asymmetric Hydrogenation of Cyclic Sulfamidate Imines: Efficient Synthesis of Chiral Cyclic Sulfamidates

Liu

Tan

et al. 2019

iScience

Self Cite

View full text Add to dashboard Cite

Summary Chiral cyclic sulfamidates are useful building blocks to construct compounds, such as chiral amines, with important applications. Often these compounds can only be generated through expensive precious metal catalysts. Here, Ni(OAc) 2 /( S , S )-Ph-BPE-catalyzed highly efficient asymmetric hydrogenation of cyclic sulfamidate imines was successfully developed, affording various chiral cyclic sulfamidates with high yields and excellent enantioselectivities (up to 99% yield, >99% enantiomeric excess [ee]). This Ni-catalyzed asymmetric hydrogenation on a gram scale has been achieved with only 0.1 mol% catalyst loading in 99% yield with 93% ee. Other types of N -sulfonyl ketimines were also hydrogenated well to obtain the corresponding products with >99% conversion, 96%–97% yields, and 97%–>99% ee. In addition, this asymmetric methodology could produce other enantioenriched organic molecules, such as chiral β-fluoroamine, amino ether, and phenylglycinol. Moreover, a reasonable catalytic cycle was provided according to the deuterium-labeling studies, which could reveal a possible mechanism for this Ni-catalyzed asymmetric hydrogenation.

show abstract

Section: Introductionmentioning

confidence: 99%

Nickel-Catalyzed Asymmetric Hydrogenation of Cyclic Sulfamidate Imines: Efficient Synthesis of Chiral Cyclic Sulfamidates

Liu

Tan

et al. 2019

iScience

Self Cite

View full text Add to dashboard Cite

show abstract

“…A novel chiral ferrocenyl bis-phosphine thiourea was introduced by Zhang and co-workers who described its use in Rh-catalyzed hydrogenation of nitroalkenes with high yields and enantioselectivities, even at low catalyst loading (Figure 25) [309,310]. This ligand, named ZhaoPhos, easily prepared from Ugi's amine, showed high efficiency in various hydrogen bond-assisted catalytic hydrogenations with rhodium and iridium complexes [311][312][313][314][315][316][317][318]. The system exemplified the idea of synergistic activation via cooperating transition metal-catalyst and organocatalyst joined in one bifunctional structure [319].…”

Section: Chiral Phosphine-bearing Thioureasmentioning

confidence: 99%

Chiral Thioureas—Preparation and Significance in Asymmetric Synthesis and Medicinal Chemistry

et al. 2020

View full text Add to dashboard Cite

For almost 20 years, thioureas have been experiencing a renaissance of interest with the emerged development of asymmetric organocatalysts. Due to their relatively high acidity and strong hydrogen bond donor capability, they differ significantly from ureas and offer, appropriately modified, great potential as organocatalysts, chelators, drug candidates, etc. The review focuses on the family of chiral thioureas, presenting an overview of the current state of knowledge on their synthesis and selected applications in stereoselective synthesis and drug development.

show abstract

“…Cyclic sulfamidates are the efficient precursors of chiral lactums, amino acids, amines and amino alcohols . Reactivity wise, these are equivalent to azetidines and aziridines.…”

Section: Synthesis Of Chiral Fused 123‐triazolesmentioning

confidence: 99%

Chiral Fused 1,2,3‐Triazoles: A Synthetic Overview

2020

View full text Add to dashboard Cite

Triazoles have always occupied a pivotal position in the field of medicinal and pharmaceutical chemistry. Recently, the area of chiral fused triazoles has gained attention. The synthetic routes to access chiral fused triazole may involve either a natural or synthetic chiral starting material with a suitably functionalized azide and alkyne component or isomer resolution to achieve chirality. Asymmetric synthesis methods using chiral complexes and organocatalysis have also emerged for obtaining chiral fused triazoles. Herein, we have described an up-to-date overview of different synthetic protocols applied to construct chiral fused 1,2,3-triazoles. Scheme 1. Basic methodologies for triazole construction. 2 3 4 5 6 7 8 . Yanai's stereo-divergent synthesis of ido-triazole ent-6 a and gluco-triazoles 7 a. Scheme 3. Yanai's diastereo-divergent synthesis of manno-, gulo-, galacto-and altro-triazoles. . Konda's synthesis of tricyclic triazolo-oxazepines 62. Scheme 15. Cobb's synthesis of spirocyclic triazolooxazine nucleosides 67. Scheme 16. Sen's synthesis of tetracyclic triazolo-oxazepines 69. to azide group and protected amine was propargylated to access azido-alkynes 122 c-h for triazole formation 124 (Scheme 29). The copper catalyzed version of this step was also carried out that gave almost approximately same yields in lesser Scheme 25. Chrandrasekaran's synthesis of triazolo-pyrazines and pyrazinones from amino acid derived sulfamidates. Scheme 26. Chrandrasekaran's synthesis of triazolo-pyrazinone 110 having pendant amino acid.structural features of triazoles, the authors carried out one pot hydrogenation and insitu Boc-protection of 155 a, followed by azidation and propargylation to afford azido-alkyne 160. Subsequently, thermal azide-alkyne cycloaddition furnished the triazole product 161 in good yield (Scheme 34).Allenyl silanes are extensively used in synthetic organic transformations and provide ready access to enantiopure pyrroles, oxiranes, furans and vinyl silanes. In lewis acid assisted reaction, allenyl silanes work as propargyl anion equivalents. Allenyl silane forms regioselective homopropargylic alcohol when treated with aldehyde and ketone. The stabilization is Scheme 31. Thomas's synthesis of steroidal fused 1,2,3-triazoles.Scheme 32. Thomas's synthesis of steroidal fused NH-1,2,3-triazoles and steroidal 4,5-fused triazolo-alkynes.

show abstract

Enantioselective Access to Chiral Cyclic Sulfamidates Through Iridium‐Catalyzed Asymmetric Hydrogenation

Cited by 16 publications

References 69 publications

Nickel-Catalyzed Asymmetric Hydrogenation of Cyclic Sulfamidate Imines: Efficient Synthesis of Chiral Cyclic Sulfamidates

Nickel-Catalyzed Asymmetric Hydrogenation of Cyclic Sulfamidate Imines: Efficient Synthesis of Chiral Cyclic Sulfamidates

Chiral Thioureas—Preparation and Significance in Asymmetric Synthesis and Medicinal Chemistry

Chiral Fused 1,2,3‐Triazoles: A Synthetic Overview

Contact Info

Product

Resources

About