3-Amino-2,6,6-trimethylbicyclo[3.1.1]heptan-2-ol

(1R,2R,3S,5R) [168286-10-0]; InChI = 1S/C10H19NO/c1-9(2)6-4-7(9)10(3,12)8(11)5-6/h6-8,12H,4-5,11H2,1-3H3/t6-,7-,8+,10+/m1/s1 InChIKey = LGVDAZQPWJBBGX-ODXREFDESA-N (1S,2S,3R,5S) [69363-09-3] C10H19NO (MW 169.26) InChI = 1S/C10H19NO/c1-9(2)6-4-7(9)10(3,12)8(11)5-6/h6-8,12H,4-5,11H2,1-3H3/t6-,7-,8+,10+/m0/s1 InChIKey = LGVDAZQPWJBBGX-QHOPCYEYSA-N (reagent used as a chiral source in stereoselective reactions) Alternate Name: ATBH, 3-amino-2-hydroxypinane Physical Data: (1R,2R,3S,5R) mp 48–49.5 °C, [α]D22 +13.1 (c 1.0, CHCl3);1 (1S,2S,3R,5S) mp 45–46.5 °C, [α]D22−14.3 (c 1.0, CHCl3).1; mp 45–47 °C; α D 20 −14.1 (c 1, CHCl3) for the (1S,2S,3R,5S) enantiomer.7 Solubility: soluble in most organic solvents; e.g. THF, CH2Cl2, CHCl3, EtOAc. Form Supplied in: colorless crystals; not commercially available. Analysis of Reagent Purity: 1H NMR, IR, elemental analysis. Preparative Methods: optically pure (1R,2R,3S,5R)-3-amino-2,6,6-trimethylbicyclo[3.1.1]heptan-2-ol (ATBH) can be prepared from optically impure (1R,5S)-α-pinene (eq 1).1 Oxidation of (1R,5S)-α-pinene (81% ee) with potassium permanganate and subsequent reaction with hydroxylamine affords the α-hydroxy oxime, which is recrystallized from ethyl ether-hexane to give the enantiomerically enriched product. Reduction of the α-hydroxy oxime with lithium aluminum hydride furnishes (1R,2R,3S,5R)-ATBH in optically pure form. (1S,2S,3R,5S)-ATBH can also be prepared in the same way from (1S,5R)-α-pinene (91% ee).1 Oxidation of (+)-α-pinene of low enantiomeric excess (∼65% ee) affords 2α-hydroxypinan-3-one, which can be upgraded to a nearly enantiopure compound via crystallization from condensed hexane solutions containing 1% (v/v) of ethylene glycol.7 (1) Purity: recrystallization from ethyl acetate-hexane. Handling, Storage, and Precautions: hygroscopic crystals. Use in a fume hood.