Trianglamine as a new chiral shift reagent for secondary alcohols

Chiral trianglamines 1 and 2 were found to be useful as NMR chiral shift reagents for the determination of enantiomeric purity and absolute configuration of several kinds of secondary alcohols, cyanohydrins, and propargyl alcohols.

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(2S,3S,12S,13S,22S,23S)-1,4,11,14,21,24-Hexaaza-(2,3:12,13:22,23)-tributano-(6,9:16,19:26,29)-trietheno-(1H,2H,3H,4H,5H,10H,11H,12H,13H,14H,15H,20H,21H,22H,23H,24H,25H)-duodecahydro-(30)-annuleneC42H60N6Ee = >99%[α]D = +82.0 (c 0.5, CHCl3)Source of chirality: (1S,2S)-diaminocyclohexaneAbsolute configuration: (2S,3S,12S,13S,22S,23S)

(2S,3S,16S,17S,30S,31S)-1,4,15,18,29,32-Hexaaza-(2,3:16,17:30,31)-tributano-(6,9:10,13:20,23:24,27:34,37:38,41)-hexaetheno-(1H,2H,3H,4H,5H,14H,15H,16H,17H,18H,19H,28H,29H,30H,31H,32H,33H,42H)-duodecahydro-(42)-annuleneC60H72N6Ee = >99%[α]D = +226 (c 1.0, CH2Cl2)Source of chirality: (1S,2S)-diaminocyclohexaneAbsolute configuration: (2S,3S,16S,17S,30S,31S)

(2S,3S,12S,13S,22S,23S)-1,4,11,14,21,24-Hexaaza-(2,3:12,13:22,23)-tributeno-(6,9:16,19:26,29)-trietheno-(2H,3H,12H,22H,23H)-hexahydro-(30)-annuleneC42H48N6Ee = >99%[α]D = +323 (c 1.0, CHCl3)Source of chirality: (1S,2S)-diaminocyclohexaneAbsolute configuration: (2S,3S,12S,13S,22S,23S)

(1S,2S)-N1,N2-Dibenzylcyclohexane-1,2-diamineC20H26N2Ee = >99%[α]D = +71.9 (c 0.5, CH2Cl2)Source of chirality: (1S,2S)-diaminocyclohexaneAbsolute configuration: (1S,2S)