Abstract:The enantioselective rhodium-catalyzed 1,2-addition of arylboronates to cyclic N-sulfamidate alkylketimines was developed. With a rhodium/diene complex as catalyst, high enantioselectivity and broad functional group tolerance were observed. The resulting sulfamidates can easily be converted into chiral β-alkyl-β-aryl amino alcohols.
“…In addition, compound 3 went through nucleophilic attack of 4-methoxyphenol, which led to chiral amino ether 5 in 76% yield (Wu et al., 2018, Nishimura et al., 2013). The hydrogenation product 2a could also be efficiently reduced with LiAlH 4 to generate ( S )-phenylglycinol 6 in 87% yield and without loss of ee value (>99% ee) (Chen et al., 2014, Liu et al., 2017), which is the key intermediate to construct chiral cyclic carbamate Evans' auxiliary (Jnoff et al., 2014) and bisoxazoline ligand ( S , S )-Ph-Box (Corey et al., 1991, Cornejo et al., 2005, Ouhamou, 2010). Scheme 4Synthetic Transformations of Product 2a…”
Section: Resultsmentioning
confidence: 99%
“…Efficient synthesis of chiral cyclic sulfamidates has attracted great attention in the past decades, owing to their versatilities working as valuable intermediates for the construction of some important organic compounds and bioactive molecules (Aguilera and Fernandez-Mayoralas, 1996, Williams et al., 2003, Bower et al., 2004, Bower et al., 2007a, Bower et al., 2007b, Bower et al., 2007c, Bower et al., 2010, Jamieson et al., 2009, Lorion et al., 2010, Megia-Fernandez et al., 2011, 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). 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 ...…”
Section: Introductionmentioning
confidence: 99%
“…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).…”
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.
“…In addition, compound 3 went through nucleophilic attack of 4-methoxyphenol, which led to chiral amino ether 5 in 76% yield (Wu et al., 2018, Nishimura et al., 2013). The hydrogenation product 2a could also be efficiently reduced with LiAlH 4 to generate ( S )-phenylglycinol 6 in 87% yield and without loss of ee value (>99% ee) (Chen et al., 2014, Liu et al., 2017), which is the key intermediate to construct chiral cyclic carbamate Evans' auxiliary (Jnoff et al., 2014) and bisoxazoline ligand ( S , S )-Ph-Box (Corey et al., 1991, Cornejo et al., 2005, Ouhamou, 2010). Scheme 4Synthetic Transformations of Product 2a…”
Section: Resultsmentioning
confidence: 99%
“…Efficient synthesis of chiral cyclic sulfamidates has attracted great attention in the past decades, owing to their versatilities working as valuable intermediates for the construction of some important organic compounds and bioactive molecules (Aguilera and Fernandez-Mayoralas, 1996, Williams et al., 2003, Bower et al., 2004, Bower et al., 2007a, Bower et al., 2007b, Bower et al., 2007c, Bower et al., 2010, Jamieson et al., 2009, Lorion et al., 2010, Megia-Fernandez et al., 2011, 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). 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 ...…”
Section: Introductionmentioning
confidence: 99%
“…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).…”
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.
“…The desired chiral cyclic sulfamidate 2 h is an important intermediate for the construction of piperazinone acid, its enantiomer was one of the two main molecular fragments containing in clinical candidate MK‐3207 . Moreover, the chiral cyclic sulfamidate 2 h was easily reduced by LiAlH 4 to generate ( S )‐difluorophenylglycinol in 92% yield and nearly without loss of ee value (92% ee) ,. The chiral difluorophenylglycinol could be further derivatized to work as new modulator of proteolytic processing of the amyloid‐β precursor proteins for Alzheimer's therapies…”
The Iridium-catalyzed asymmetric hydrogenation of cyclic sulfamidate imines was successfully developed with N-methylated ZhaoPhos L2 as the ligand. A variety of chiral cyclic sulfamidates were obtained with excellent results (up to 99% yield, 99% ee). Furthermore, this asymmetric hydrogenation can be employed as the key reaction step to prepare the important intermediates in organic synthesis.
“…3a,4 Furthermore, Feng and co-workers recently reported the rhodium-catalyzed addition of arylboronates to cyclic Nsulfamidate alkylketimine as an efficient method for the preparation of β-aryl-β-amino alcohols bearing a tetra-substituted carbon center. 5 However, in most cases, these synthetic methods are only suitable for acyclic β-amino alcohols containing a tetrasubstituted carbon center bearing a nitrogen, 3a,4-7 with the synthesis of the corresponding cyclic β-amino alcohols remaining a significant challenge. Herein, we report a new process for the sequential [3,3]sigmatropic rearrangement/nucleophilic addition of N-(benzoyloxy)enamides 1 as a strategy for the synthesis of βaryl-β-amino alcohol derivatives 3 bearing a tetrasubstituted carbon center (Scheme 1, top).…”
A new method has been developed for the efficient synthesis of cyclic β-aryl-β-amino alcohol derivatives bearing a tetrasubstituted carbon center via the [3,3]-sigmatropic rearrangement of N-(benzoyloxy)enamides followed by nucleophilic arylation reaction with a range of triarylaluminum reagents. The resulting products were converted into the corresponding sterically congested cyclic β-amino alcohols, as well as the dissociative anesthetic agent Tiletamine.
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