benzyl 3,7-diazabicyclo[4.1.0]heptane-3-carboxylate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of benzyl 3,7-diazabicyclo[4.1.0]heptane-3-carboxylate (1.0 equiv.) in DCM (0.26M) was added diethyl phosphorochloridate (1.3 equiv.) and triethyl amine (1.5 equiv.). The reaction was stirred for 24 h, then concentrated to dryness. Added water and ethyl acetate, the organics were extracted, dried with Na2SO4, and concentrated. The crude was purified via silica gel column chromatography eluting with ethyl acetate and hexanes (50% to 100% ethyl acetate) to yield benzyl 7-(diethoxyphosphoryl)-3,7-diazabicyclo[4.1.0]heptane-3-carboxylate as a clear oil in 21% yield. LCMS (m/z): 369.0 (MH+). concentrated to dryness Added water and ethyl acetate, the organics were extracted dried with Na2SO4 concentrated The crude was purified via silica gel column chromatography eluting with ethyl acetate and hexanes (50% to 100% ethyl acetate)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of benzyl 3-azido-4-hydroxypiperidine-1-carboxylate and benzyl 4-azido-3-hydroxypiperidine-1-carboxylate (1.0 equiv.) in dioxane (0.14M) was added PPh3 (2.0 equiv.) and the reaction was heated to reflux for 1 h. The solution was then concentrated under vacuo and purified via silica gel column chromatography eluting with DCM, 10% MeOH and 1% Et3N to give benzyl 3,7-diazabicyclo[4.1.0]heptane-3-carboxylate as a clear oil in 25% yield. LCMS (m/z): 233.0 (MH+), Rt=1.94 min. the reaction was heated to reflux for 1 h The solution was then concentrated under vacuo purified via silica gel column chromatography eluting with DCM, 10% MeOH and 1% Et3N

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of benzyl 3,7-diazabicyclo[4.1.0]heptane-3-carboxylate (1.0 equiv.) in DCM (0.26M) was added diethyl phosphorochloridate (1.3 equiv.) and triethyl amine (1.5 equiv.). The reaction was stirred for 24 h, then concentrated to dryness. Added water and ethyl acetate, the organics were extracted, dried with Na2SO4, and concentrated. The crude was purified via silica gel column chromatography eluting with ethyl acetate and hexanes (50% to 100% ethyl acetate) to yield benzyl 7-(diethoxyphosphoryl)-3,7-diazabicyclo[4.1.0]heptane-3-carboxylate as a clear oil in 21% yield. LCMS (m/z): 369.0 (MH+). concentrated to dryness Added water and ethyl acetate, the organics were extracted dried with Na2SO4 concentrated The crude was purified via silica gel column chromatography eluting with ethyl acetate and hexanes (50% to 100% ethyl acetate)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of benzyl 3-azido-4-hydroxypiperidine-1-carboxylate and benzyl 4-azido-3-hydroxypiperidine-1-carboxylate (1.0 equiv.) in dioxane (0.14M) was added PPh3 (2.0 equiv.) and the reaction was heated to reflux for 1 h. The solution was then concentrated under vacuo and purified via silica gel column chromatography eluting with DCM, 10% MeOH and 1% Et3N to give benzyl 3,7-diazabicyclo[4.1.0]heptane-3-carboxylate as a clear oil in 25% yield. LCMS (m/z): 233.0 (MH+), Rt=1.94 min. the reaction was heated to reflux for 1 h The solution was then concentrated under vacuo purified via silica gel column chromatography eluting with DCM, 10% MeOH and 1% Et3N