Efficient synthesis of chiral β- and γ-N-tosylaminoalcohols from 1-aryl-2-aminopropane-1,3-diols

Article abstract of DOI:10.1134/S107042800604004X

(1S,2S)-1-Aryl-2-tozylaminopropan-1-ols were synthesized by cyclization of 1-aryl-2-aminopropane-1,3-diol to aryl(1-tosylaziridin-2-yl)methanols, followed by hydride reduction of the latter. Reduction of the aza-Payne rearrangement products of intermediat

Full text of DOI:10.1134/S107042800604004X

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ꢊꢋꢎꢏꢃWꢃꢄꢅ+ꢆꢃ&+ 27VꢈꢆꢃꢀꢋꢅꢇꢃVꢃꢄꢅ+ꢈꢆꢃꢀꢋꢂꢍꢃVꢃꢄꢅ+ꢈꢆꢃꢓꢋꢀꢎꢃGꢃ LQꢃꢇꢏꢃPOꢃRIꢃDFHWRQLWULOHꢃZDVꢃKHDWHGꢃIRUꢃꢇꢃKꢃDWꢃꢓꢏ±ꢓꢓƒ&ꢃ
ꢄꢅ+ꢆꢃ&+2+ꢆꢃ-ꢃ ꢃꢓꢋꢅꢃ+]ꢈꢃꢍꢋꢏꢂꢃGꢃꢄꢇ+ꢆꢃ-ꢃ ꢃꢎꢋꢀꢃ+]ꢈꢆꢃꢃ RQꢃ Dꢃ ZDWHUꢃ EDWKꢆꢃ DQGꢃ WKHꢃVROYHQWꢃ ZDVꢃUHPRYHGꢃ XQGHUꢃ
ꢍꢋꢅꢊꢃGꢃꢄꢇ+ꢆꢃ-ꢃ ꢃꢎꢋꢍꢃ+]ꢈꢆꢃꢍꢋꢊꢏꢃGꢃꢄꢇ+ꢆꢃ-ꢃ ꢃꢎꢋꢀꢃ+]ꢈꢆꢃꢍꢋꢀꢅꢃGꢃ
ꢄꢇ+ꢆꢃ-ꢃ ꢃꢎꢋꢍꢃ+]ꢈꢆꢃꢍꢋꢂꢂꢃGꢃꢄꢇ+ꢆꢃ-ꢃ ꢃꢎꢋꢅꢃ+]ꢈꢆꢃꢍꢋꢁꢎꢃGꢃꢄꢇ+ꢆꢃꢃ
-ꢃ ꢃꢎꢋꢅꢃ+]ꢈꢋꢃ
UHGXFHGꢃSUHVVXUHꢋꢃꢃ
>ꢂꢁꢉꢋꢁ0HWK\OSKHQ\OVXOIRQ\OꢊD]LULGLQꢁꢃꢁ\O@ꢁꢀ
ꢉꢋꢁQLWURSKHQ\OꢊPHWKDQROꢀ ꢉ,9Dꢊꢈꢃ$IWHUꢃWUHDWPHQWꢃRIꢃ
ꢓꢋꢇꢅꢃJꢃꢄꢅꢏꢋꢏꢃPPROꢈꢃRIꢃꢄꢅ6ꢆꢇ6ꢈꢉꢇꢉꢄꢀꢉPHWK\OSKHQ\OVXOꢉ
IRQ\ODPLQRꢈꢉꢊꢉꢄꢀꢉPHWK\OSKHQ\OVXOIRQ\OR[\ꢈꢉꢅꢉꢃ
ꢄꢀꢉQLWURSKHQ\OꢈSURSDQꢉꢅꢉROꢃ ꢄ,,Dꢈꢃ ZLWKꢃ SRWDVVLXPꢃ FDUꢉ
ERQDWHꢃDFFRUGLQJꢃWRꢃWKHꢃJHQHUDOꢃSURFHGXUHꢆꢃWKHꢃSUHFLSꢉ
LWDWHꢃZDVꢃILOWHUHGꢃRIIꢃDQGꢃZDVKHGꢃZLWKꢃZDWHUꢋꢃ<LHOGꢃ
ꢊꢋꢊꢅꢃJꢃꢄꢁꢓꢃLꢈꢆꢃZKLWHꢃVROLGꢆꢃPSꢃꢅꢎꢇ±ꢅꢎꢀƒ&ꢆꢃ> @ ꢃ ꢃꢃ
±ꢓꢋꢏꢃ ꢄFꢃ ꢃ ꢅꢋꢏꢆꢃ &+ 2+ꢈꢋꢃ ,5ꢃ VSHFWUXPꢆꢃ ꢆꢃ FP ꢑꢃ ꢊꢀꢍꢍꢆꢃ
ꢅꢂꢏꢏꢆꢃꢅꢓꢅꢀꢆꢃꢅꢊꢀꢓꢆꢃꢅꢊꢏꢍꢆꢃꢅꢅꢓꢓꢆꢃꢁꢊꢎꢆꢃꢎꢊꢓꢆꢃꢍꢇꢁꢋꢃ +ꢃ105ꢃ
VSHFWUXPꢃꢄ'062ꢉG ꢈꢆꢃ ꢆꢃSSPꢑꢃꢇꢋꢊꢇꢃVꢃꢄ2+ꢈꢆꢃꢇꢋꢀꢇꢃVꢃꢄꢊ+ꢆꢃ
&+ ꢈꢆꢃꢇꢋꢓꢇꢃGꢃꢄꢅ+ꢆꢃꢊꢉ+ꢆꢃ-ꢃ ꢃꢀꢋꢓꢃ+]ꢈꢆꢃꢇꢋꢍꢍꢃGꢃꢄꢅ+ꢆꢃꢊꢉ+ꢆꢀꢀ
-ꢃ ꢃꢂꢋꢂꢃ+]ꢈꢆꢃꢊꢋꢏꢊꢃWꢃꢄꢅ+ꢆꢃꢇꢉ+ꢆꢃ-ꢃ ꢃꢊꢋꢊꢃ+]ꢈꢆꢃꢀꢋꢍꢅꢃWꢃꢄꢅ+ꢆꢃ
&+2+ꢆꢃ-ꢃ ꢃꢓꢋꢅꢃ+]ꢈꢆꢃꢍꢋꢇꢏꢃGꢃꢄꢇ+ꢆꢃ-ꢃ ꢃꢎꢋꢅꢃ+]ꢈꢆꢃꢍꢋꢊꢓꢃGꢃ
ꢄꢇ+ꢆꢃ-ꢃ ꢃꢎꢋꢍꢃ+]ꢈꢆꢃꢍꢋꢂꢇꢃGꢃꢄꢇ+ꢆꢃ-ꢃ ꢃꢎꢋꢅꢃ+]ꢈꢆꢃꢎꢋꢏꢊꢃGꢃꢄꢇ+ꢆꢃꢃ
-ꢃ ꢃꢎꢋꢅꢃ+]ꢈꢋꢃ &ꢃ105ꢃVSHFWUXPꢃꢄ'062ꢉG ꢈꢆꢃ ꢆꢃSSPꢑꢃ
ꢇꢏꢋꢍꢃꢄ&+ ꢈꢒꢃꢇꢁꢋꢇꢃꢄ& ꢈꢒꢃꢀꢓꢋꢊꢃꢄ& ꢈꢒꢃꢂꢁꢋꢊꢃꢄ&+2+ꢈꢒꢃꢅꢇꢊꢋꢇꢆꢃ
ꢅꢇꢍꢋꢇꢆꢃꢅꢇꢎꢋꢅꢆꢃꢅꢇꢁꢋꢍꢆꢃꢅꢊꢓꢋꢇꢆꢃꢅꢀꢀꢋꢍꢆꢃꢅꢀꢍꢋꢊꢆꢃꢅꢀꢁꢋꢍꢃꢄ& ꢈꢋꢃ
0DVVꢃVSHFWUXPꢆꢃPꢐ]ꢑꢃꢊꢀꢁꢃ>0ꢃꢔꢃꢅ@ ꢆꢃꢅꢎꢀꢃ>&+ 1+7V@ ꢋꢃꢃ
>ꢂꢁꢉꢋꢁ0HWK\OSKHQ\OVXOIRQ\OꢊD]LULGLQꢁꢃꢁ\O@ꢁ
SKHQ\OPHWKDQROꢀ ꢉ,9Eꢊꢈꢃ)ROORZLQJꢃWKHꢃJHQHUDOꢃSURFHꢉ
GXUHꢆꢃWKHꢃUHDFWLRQꢃRIꢃꢀꢋꢍꢂꢃJꢃꢄꢅꢏꢋꢏꢃPPROꢈꢃRIꢃFRPSRXQGꢃ
,,Eꢃ ZLWKꢃ SRWDVVLXPꢃ FDUERQDWHꢃ JDYHꢃ DQꢃRLO\ꢃ SURGXFWꢃ
ZKLFKꢃZDVꢃH[WUDFWHGꢃZLWKꢃGLHWK\OꢃHWKHUꢋꢃ7KHꢃH[WUDFWꢃ
ZDVꢃZDVKHGꢃZLWKꢃVDWXUDWHGꢃVROXWLRQVꢃRIꢃ1D+&2 ꢃDQGꢃ
1D&Oꢃ DQGꢃ GULHGꢃ RYHUꢃ 0J62 ꢆꢃ DQGꢃ WKHꢃ VROYHQWꢃ ZDVꢃ
UHPRYHGꢋꢃ7KHꢃUHVLGXHꢃZDVꢃDꢃVWLFN\ꢃPDWHULDOꢃZKLFKꢃZDVꢃ
GULHGꢃXQGHUꢃUHGXFHGꢃSUHVVXUHꢋꢃ<LHOGꢃꢇꢋꢍꢇꢃJꢃꢄꢁꢏLꢈꢆꢃ
ZKLWHꢃVROLGꢆꢃPSꢃꢎꢇ±ꢎꢊƒ&ꢆꢃ> @ ꢃ ꢃ±ꢅꢇꢋꢓƒꢃꢄFꢃ ꢃꢅꢋꢏꢆꢃ
&+ 2+ꢈꢋꢃ,5ꢃVSHFWUXPꢆꢃ ꢆꢃFP ꢑꢃꢊꢀꢍꢂꢃꢅꢓꢁꢍꢆꢃꢅꢀꢓꢇꢆꢃ
ꢅꢊꢅꢂꢆꢃ ꢅꢅꢂꢏꢆꢃ ꢅꢏꢎꢁꢆꢃ ꢁꢀꢊꢆꢃ ꢎꢊꢍꢋꢃ +ꢃ 105ꢃ VSHFWUXP ꢃ
ꢄ&'&O ꢈꢆꢃ ꢆꢃSSPꢑꢃꢇꢋꢇꢅꢃVꢃꢄ2+ꢈꢆꢃꢇꢋꢀꢏꢃGꢃꢄꢅ+ꢆꢃꢊꢉ+ꢆꢃ-ꢃ ꢃꢃ
ꢀꢋꢓꢃ+]ꢈꢆꢃꢇꢋꢀꢀꢃVꢃꢄꢊ+ꢆꢃ&+ ꢈꢆꢃꢇꢋꢍꢏꢃGꢃꢄꢅ+ꢆꢃꢊꢉ+ꢆꢀ-ꢃ ꢃꢃ
ꢍꢋꢇꢃ +]ꢈꢆꢃ ꢊꢋꢏꢍꢃ Wꢃ ꢄꢅ+ꢆꢃ ꢇꢉ+ꢆꢀ -ꢃ ꢃ ꢓꢋꢀꢃ +]ꢈꢆꢃ ꢀꢋꢀꢂꢃ Wꢃ ꢄꢅ+ꢆꢃ
ꢉꢂ6ꢄꢃ6ꢊꢁꢃꢁꢉꢋꢁ0HWK\OSKHQ\OVXOIRQ\ODPLQRꢊꢁꢅꢁꢉꢋꢁ
PHWK\OVXOIRQ\OR[\ꢊꢁꢂꢁSKHQ\OSURSDQꢁꢂꢁROꢀ ꢉ,,Eꢊꢃ ZDVꢃ
V\QWKHVL]HGꢃ DFFRUGLQJꢃ WRꢃ WKHꢃ JHQHUDOꢃ SURFHGXUHꢃ IURPꢃ
ꢅꢋꢂꢍꢃJꢃꢄꢅꢏꢋꢏꢃPPROꢈꢃRIꢃꢇꢉDPLQRꢉꢅꢉSKHQ\OSURSDQHꢉꢅꢆꢊꢉ
GLROꢃ ꢄ,Eꢈꢃ DQGꢃ ꢊꢋꢎꢇꢃ Jꢃ ꢄꢇꢃ HTXLYꢈꢃ RIꢃ SꢉWROXHQHVXOIRQ\Oꢃ
FKORULGHꢋꢃ<LHOGꢃꢊꢋꢎꢓꢃJꢃꢄꢎꢅLꢈꢆꢃRIIꢉZKLWHꢃVROLGꢆꢃPSꢃꢅꢊꢊ±
ꢅꢊꢀƒ&ꢆꢃ> @ ꢃ ꢃꢔꢍꢀƒꢃꢄFꢃ ꢃꢅꢋꢏꢆꢃ&+ 2+ꢈꢋꢃ,5ꢃVSHFWUXPꢆꢃ ꢆꢃ
FP ꢑꢃꢊꢀꢁꢓꢆꢃꢊꢀꢓꢊꢆꢃꢊꢇꢁꢂꢆꢃꢅꢓꢁꢎꢆꢃꢅꢊꢂꢂꢆꢃꢅꢅꢓꢇꢆꢃꢁꢍꢎꢆꢃꢎꢊꢓꢆꢃ
ꢎꢏꢍꢆꢃꢍꢀꢎꢋꢃ +ꢃ105ꢃVSHFWUXPꢃꢄ'062ꢉG ꢈꢆꢃ ꢆꢃSSPꢑꢃꢃ
ꢇꢋꢊꢇꢃ Vꢃ ꢄꢊ+ꢆꢃ &+ ꢈꢆꢃ ꢇꢋꢀꢀꢃ Vꢃ ꢄꢊ+ꢆꢃ &+ ꢈꢆꢃ ꢊꢋꢀꢀꢃ Pꢃ ꢄꢅ+ꢆꢃ
&+1+ꢈꢆꢃꢊꢋꢂꢊꢃWꢃꢄꢅ+ꢆꢃ&+ 27VꢈꢆꢃꢀꢋꢏꢁꢃWꢃꢄꢅ+ꢆꢃ&+ 27Vꢈꢆꢃ
ꢀꢋꢂꢍꢃVꢃꢄꢅ+ꢈꢆꢃꢓꢋꢂꢀꢃGꢃꢄꢅ+ꢆꢃ&+2+ꢆꢃ-ꢃ ꢃꢓꢋꢅꢃ+]ꢈꢃꢍꢋꢅꢊꢃ Gꢃ
ꢄꢂ+ꢆꢃ-ꢃ ꢃꢎꢋꢍꢃ+]ꢈꢆꢃꢍꢋꢊꢓꢃGꢃꢄꢇ+ꢆꢃ-ꢃ ꢃꢂꢋꢁꢃ+]ꢈꢆꢃꢍꢋꢀꢂꢃGꢃꢄꢇ+ꢆꢀꢀ
-ꢃ ꢃꢎꢋꢅꢃ+]ꢈꢆꢃꢍꢋꢂꢀꢃWꢃꢄꢊ+ꢈꢋꢃ
ꢉꢂ6ꢄꢃ6ꢊꢁꢃꢁꢉꢋꢁ0HWK\OSKHQ\OVXOIRQ\ODPLQRꢊꢁꢂꢁꢉꢋꢁ
QLWURSKHQ\OꢊSURSDQHꢁꢂꢄꢅꢁGLROꢀ ꢉ,,,DꢊꢃZDVꢃV\QWKHVL]HGꢃ
DFFRUGLQJꢃWRꢃWKHꢃJHQHUDOꢃSURFHGXUHꢃIURPꢃꢇꢋꢅꢇꢃJꢃꢃ
ꢄꢅꢏꢋꢏꢃPPROꢈꢃRIꢃꢇꢉDPLQRꢉꢅꢉꢄꢀꢉQLWURSKHQ\OꢈSURSDQHꢉꢅꢆꢊꢉ
GLROꢃꢄ,Dꢈꢃ DQGꢃ ꢅꢋꢁꢅꢃ Jꢃ ꢄꢅꢃ HTXLYꢈꢃRIꢃ SꢉWROXHQHVXOIRQ\Oꢃ
FKORULGHꢋꢃ <LHOGꢃ ꢊꢋꢓꢅꢃ Jꢃ ꢄꢁꢂLꢈꢆꢃ ZKLWHꢃ VROLGꢆꢃ PSꢃ ꢇꢀꢀ±
ꢇꢀꢂƒ&ꢃꢄGHFRPSꢋꢈꢆꢃ> @ ꢃ ꢃꢔꢇꢁꢋꢓƒꢃꢄFꢃ ꢃꢅꢋꢏꢆꢃ&+ 2+ꢈꢋꢃ,5ꢃ
VSHFWUXPꢆꢃ ꢆꢃFP ꢑꢃꢊꢀꢍꢀꢆꢃꢊꢊꢇꢊꢆꢃꢊꢇꢂꢎꢆꢃꢅꢂꢏꢊꢆꢃꢅꢓꢅꢁꢆꢃ
ꢅꢊꢀꢓꢆꢃ ꢅꢅꢀꢁꢆꢃ ꢅꢏꢍꢇꢆꢃꢎꢓꢊꢆꢃ ꢎꢅꢇꢋꢃ +ꢃ105ꢃVSHFWUXPꢃ
ꢄ'062ꢉG ꢈꢆꢃ ꢆꢃ SSPꢑꢃ ꢇꢋꢇꢓꢃ Vꢃ ꢄꢊ+ꢆꢃ &+ ꢈꢆꢃ ꢊꢋꢓꢓꢃ Pꢃ ꢄꢅ+ꢆꢃ
&+1+ꢈꢆꢃꢀꢋꢎꢂꢃPꢃꢄꢅ+ꢆꢃ&+ 2+ꢈꢆꢃꢀꢋꢁꢁꢃPꢃꢄꢅ+ꢆꢃ&+ 2+ꢈꢆꢃ
ꢓꢋꢂꢁꢃGꢃꢄꢅ+ꢆꢃ&+2+ꢆꢃ-ꢃ ꢃꢓꢋꢅꢃ+]ꢈꢆꢃꢍꢋꢏꢂꢃGꢃꢄꢇ+ꢆꢃ-ꢃ ꢃꢃ
ꢍꢋꢎꢃ+]ꢈꢆꢃꢍꢋꢊꢏꢃGꢃꢄꢇ+ꢆꢃ-ꢃ ꢃꢎꢋꢅꢃ+]ꢈꢆꢃꢍꢋꢀꢏꢃGꢃꢄꢇ+ꢆꢃ-ꢃ ꢃꢃ
ꢎꢋꢀꢃ+]ꢈꢆꢃꢍꢋꢁꢇꢃGꢃꢄꢇ+ꢆꢃ-ꢃ ꢃꢎꢋꢀꢃ+]ꢈꢋꢃ
ꢉꢂ6ꢄꢃ6ꢊꢁꢃꢁꢉꢋꢁ0HWK\OSKHQ\OVXOIRQ\ODPLQRꢊꢁꢂꢁ
SKHQ\OSURSDQHꢁꢂꢄꢅꢁGLROꢀ ꢉ,,,Eꢊꢃ ZDVꢃ V\QWKHVL]HGꢃ
DFFRUGLQJꢃWRꢃWKHꢃJHQHUDOꢃSURFHGXUHꢃIURPꢃꢅꢋꢂꢍꢃJꢃꢃ
ꢄꢅꢏꢋꢏꢃPPROꢈꢃRIꢃꢇꢉDPLQRꢉꢅꢉSKHQ\OSURSDQHꢉꢅꢆꢊꢉGLROꢃꢄ,Eꢈꢃ
DQGꢃ ꢅꢋꢁꢅꢃ Jꢃ ꢄꢅꢃ HTXLYꢈꢃRIꢃSꢉWROXHQHVXOIRQ\OꢃFKORULGHꢋꢃ
<LHOGꢃ ꢇꢋꢎꢁꢃ Jꢃ ꢄꢁꢏLꢈꢆꢃ RIIꢉZKLWHꢃ VROLGꢆꢃ PSꢃ ꢅꢓꢎ±ꢅꢂꢏƒ&ꢆꢃ
> @ ꢃ ꢃꢔꢓꢅƒꢃꢄFꢃ ꢃꢅꢋꢏꢆꢃ&+ 2+ꢈꢋꢃ,5ꢃVSHFWUXPꢆꢃ ꢆꢃFP ꢑꢃ
ꢊꢀꢁꢎꢆꢃ ꢊꢀꢀꢊꢆꢃ ꢊꢇꢀꢊꢆꢃ ꢅꢀꢇꢍꢆꢃ ꢅꢊꢏꢎꢆꢃ ꢅꢏꢎꢍꢆꢃ ꢎꢇꢓꢆꢃ ꢍꢓꢂꢋꢃꢃ
+ꢃ 105ꢃ VSHFWUXPꢃ ꢄ'062ꢉG ꢈꢆꢃ ꢆꢃ SSPꢑꢃ ꢇꢋꢊꢊꢃ Vꢃ ꢄꢊ+ꢆꢃ
&+ ꢈꢆꢃꢊꢋꢅꢇꢃWꢃꢄꢅ+ꢆꢃ&+ 2+ꢈꢆꢃꢊꢋꢇꢂꢃPꢃꢄꢅ+ꢆꢃ&+1+ꢈꢃꢊꢋꢀꢊꢃWꢃ
ꢄꢅ+ꢆꢃ&+ 2+ꢈꢆꢃꢀꢋꢎꢀꢃGꢃꢄꢅ+ꢆꢃ&+2+ꢆꢃ-ꢃ ꢃꢓꢋꢀꢃ+]ꢈꢆꢃꢍꢋꢏꢎꢃGꢃ
ꢄꢇ+ꢆꢃ-ꢃ ꢃꢎꢋꢀꢃ+]ꢈꢆꢃꢍꢋꢅꢍꢃWꢃꢄꢓ+ꢈꢆꢃꢍꢋꢀꢊꢃGꢃꢄꢇ+ꢆꢃ-ꢃ ꢃꢎꢋꢅꢃ+]ꢈꢋꢃ
&+2+ꢆꢀ-ꢃ ꢃꢓꢋꢀꢃ+]ꢈꢆꢃꢍꢋꢇꢓ±ꢍꢋꢇꢍꢃPꢃꢄꢍ+ꢆꢃ+
ꢍꢋꢍꢀꢃGꢃꢄꢇ+ꢆꢃ+ ꢈꢋꢃ &ꢃ105ꢃVSHFWUXPꢃꢄ&'&O ꢈꢆꢃ ꢆꢃ
ꢈꢆꢃꢍꢋꢍꢅ±
SSPꢑꢃꢇꢅꢋꢁꢃꢄ&+ ꢈꢆꢃꢊꢅꢋꢅꢃꢄ& ꢈꢒꢃꢀꢓꢋꢀꢃꢄ& ꢈꢒꢃꢍꢇꢋꢍꢃꢄ&+2+ꢈꢒꢃ
ꢅꢇꢂꢋꢇꢆꢃꢅꢇꢎꢋꢊꢆꢃꢅꢇꢎꢋꢎꢆꢃꢅꢊꢏꢋꢏꢆꢃꢅꢊꢀꢆꢃꢅꢀꢏꢋꢇꢆꢃꢅꢀꢓꢋꢏꢃꢄ& ꢈꢋꢃ
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ꢇꢏꢏꢏꢆꢃYROꢋꢃꢀꢅꢆꢃSꢋꢃꢀꢂꢍꢍꢋꢃ
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