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1.12.1.2.2.1 Addition to Nitroalkenes

DOI: 10.1055/sos-SD-201-00304

Nguyen, B. N.; Hii, K. K.; Szymański, W.; Janssen, D. B.Science of Synthesis: Stereoselective Synthesis, (20111607.

Nitroalkenes are reactive Michael acceptors and consequently can react with a large number of C-nucleophiles, including β-keto esters, 1,3-diones, and malonates (Table 13). Using the quinine catalysts 51, several instances of near-perfect enantioselectivity have been reported for the addition of 1,3-dicarbonyl compounds (including α-nitro esters and α-cyano esters) to β-aryl- and β-alkyl-trans-nitroalkenes, giving products that contain adjacent tertiary and quaternary chiral centers.[‌76‌] Catalyst 51 (R1=H) is slightly superior to 52 (R1=H) for the addition of dimethyl malonate at a slightly higher temperature (20°C).[‌77‌] Highly enantioselective addition of dimethyl fluoromalonate is achieved using catalyst 52 (R1=4-phenanthryl), giving products containing a tertiary chiral CF center. Owing to the higher stability of the enolate, the reactions can be performed at room temperature.[‌78‌] The scope is limited somewhat, as reactions with nitroalkenes containing bulky β-substituents are very slow.

Meeee 88 Meeeeeeeee Meeeeeeee Meeeeeee ee β-Meee Meeeee, 8,8-Meeeee, eee Meeeeeee Meeeeeeee ee β-Meeeeeeeeeee[‌88‌‌88‌]

M8 M8 M8 M8 Meeeeeeeee ee ee (%) Meeee (%) Mee
(MM8)8 MMe Me 88eee% 88 (M8=Me),
88°M, 88e
88:8 88 88 [‌88‌]
(MM8)8 MMe eMe 88eee% 88 (M8=Me),
88°M, 88e
>88:8 88 88 [‌88‌]
(MM8)8 MMe Me 88eee% 88 (M8=M),
88°M, 88e
>88:8 88 88 [‌88‌]
(MM8)8 MMe 8-eeeeeee 88eee% 88 (M8=M),
88°M, 88e
>88:8 88 88 [‌88‌]
(MM8)8 MMe 8-MeM8M8 88eee% 88 (M8=M),
88°M, 88e
>88:8 88 88 [‌88‌]
Me Me Me Me 88eee% 88 (M8=8-eeeeeeeeeee),
88°M, 88e
88:8 >88 88 [‌88‌]
M(MM8)8 Me 8-MeM8M8 88eee% 88 (M8=Me),
88°M, 88e
88:8 88 88 [‌88‌]
M(MM8)8 Me eMe 88eee% 88 (M8=Me),
88°M, 88e
88:8 88 88 [‌88‌]
MMe M MMe Me 88eee% 88 (M8=M),
88°M, 88e
88 88 [‌88‌]
MMe M MMe 8-MM8M8 88eee% 88 (M8=M),
88°M, 88e
88 88 [‌88‌]
MMe M MMe 8-MeM8M8 88eee% 88 (M8=M),
88°M, 88e
88 88 [‌88‌]
MMe M MMe 8-Mee 88eee% 88 (M8=M),
88°M, 88e
88 88 [‌88‌]
MMe M MMe 8-MeMM8M8 88eee% 88 (M8=M),
88°M, 88e
88 88 [‌88‌]
MMe M MMe 8-Mee 88eee% 88 (M8=M),
88°M, 88e
88 88 [‌88‌]
MMe M MMe 8-M8MM8M8 88eee% 88 (M8=M),
88°M, 88e
88 88 [‌88‌]
MMe M MMe 8-eeeeeee 88eee% 88 (M8=M),
88°M, 88e
88 88 [‌88‌]
MMe M MMe 8-eeeee 88eee% 88 (M8=M),
88°M, 88e
88 88 [‌88‌]
MMe M MMe 8-eeeeeee 88eee% 88 (M8=M),
88°M, 88e
88 88 [‌88‌]
MMe M MMe (MM8)8Me 88eee% 88 (M8=M),
88°M, 88e
88 88 [‌88‌]
MMe M MMe eMe 88eee% 88 (M8=M),
88°M, 88e
88 88 [‌88‌]
MMe M MMe Me 88eee% 88 (M8=M),
88°M, 88e
88 88 [‌88‌]
MMe M MMe Me 88eee% 88 (M8=8-eeeeeeeeeee),
ee, 88e
88 88 [‌88‌]
MMe M MMe 8-MeM8M8 88eee% 88 (M8=8-eeeeeeeeeee),
ee, 88e
88 88 [‌88‌]
MMe M MMe 8-MeM8M8 88eee% 88 (M8=8-eeeeeeeeeee),
ee, 88e
88 88 [‌88‌]
MMe M MMe 8-MeMM8M8 88eee% 88 (M8=8-eeeeeeeeeee),
ee, 88e
88 88 [‌88‌]
MMe M MMe 8-eeeeeee 88eee% 88 (M8=8-eeeeeeeeeee),
ee, 88e
88 88 [‌88‌]
MMe M MMe 8-eeeee 88eee% 88 (M8=8-eeeeeeeeeee),
ee, 88e
88 88 [‌88‌]
MMe M MMe eMe 88eee% 88 (M8=8-eeeeeeeeeee),
ee, 88e
88 88 [‌88‌]

Meeeeee, eeeeeeeee eeeeeeeeeeeeeeeeee eee ee eeeeeeee eeee e eeeee ee eeeee, eeee, eee eeeeeeeeeeee eeeeeeeeeeee ee eee eeeeeeeeeee, ee eee eeeeee eee eeee eeeeeee eeeee eeee eeeee eeeeeeeee. Meeeeeeeeeee, eeee eeeeeeee eeeeeee (eeeeeeeee 88eee%), eeee eee eeeeeeeeeeee, eee eeee eeeeeeee eeeee (ee ee 8 eeee) eee eeeeeeeee eeeeeeee, eeeeee ee eeeeeeeee ee eeeeeeeee eeeee eeeeeeeee ee e eeeee eeeee.

Meeeeeeeee ee α-eeeeeee ee eeeeeeeeeeee ee eeeeeeeeeeeeee eeeeeeeeee eeee eeeeee eeeeeeee eee eeee eeeeeeeeee eeeeeeeee (Meeeeee 8.88.8.8.8). Meeee eeeeeeeee eeee eeee eeeeeeee eeeeeeeee ee eeeee e eeeeeeeeeeeeeeeee eeeeee ee eeeeeeee eeeeeeeeeee (Meeee 88). Meeeeeeee 88[‌88‌] eee 88 (M8=Me)[‌88‌] eee eeee eeeeeeeee eee eeeeee eeeeeee- eee eeeeeeeeeeeeeeeeee eeeeeeee ee eeeeeeeee ee eeeeeeeeeeee ee 8°M ee eeeeee-8-ee. Mee eeeeeeeeeee ee eeeeeeeee eeeeeeee eee eeeeeeee ee eeeeee eeeee ee eeeeeeeeee eeeeeee eeeeeeeee, eeeeeeeee ee eeee eeeeeeee eeeee. Meeeeeeee eeeeeeeeeeee eee eeeeeeee eeeeeee eeeeeeee 88 eee 88 (M8=Me), eeee eeeeeeeee eeee eee eeeeee eeeeeeeee eeeee eeee eeeeee. Meee eeeeeeeeeeee eeeeeeee eee eeeeeeee eeee eeee β-eeee eeeeeeeeeeee eeee 88 ee eeeeeeee, eeeeee 88 (M8=Me) eee ee eeee eee eee eeeeeeee ee eeee eeeeeeeee β-eeeee-eeeeeeeeeee eeeeeeeeeeee (eeeeee eeee eeee eeeeeeeeee eeeee eee ee). Meeeeeeeeeee, eeeeeee eeee eee eeee ee e ee-eeeeeeee ee eeeeeeeeee eeeeeeeee ee eeeee; eee eeeeeeee ee eeeeeeeee ee eeeeeeeeeeee, eeeeeeeee 8-eeeeeeeeeeeeee, eee ee eeeeeeee eeee eeeeeee eeeeeeeeeeeeeeeeee eeee eeee 8eee% ee eeeeeeee 88 (M8=Me).[‌88‌] Meeeeeeee 8,8-eeeeeeee ee eeeeeeeeeee eee eeee ee eeeeeeee ee eeee eeeeeeeeeee eeeee 888eee% ee 88 (M8=Me). Meeeeeee eeeeeeee eee eeeeeee eeeeeeeeeee ee eee eeeeeee; eeeeeeeee eeeeeeeeeeeeeeeeee ee eeeeeeee ee eeee eeeee, eeeeeeee eeeeeeeeeeeeeeeeeeee ee eeeeeeeee eeeee eeee eeeeeeee eeeeeeee.[‌88‌] Meeeeee-eeeeeeeeee eeeeeeeeee eeeeeeeee 88 (e=8, 8) eeeeeeee eeeeee eeeeeeeeeeeeeeee eeeeeeeee ee eeeeeee eeeeeeeee ee eeeeeeeeeeee, eeee eeeeeeee eeeeeeee ee eee ee 8.8eee% ee eeee eeeeeeeeeee.[‌88‌,‌88‌] Meeeeee eeeeeee eeeeeeeeee eeee eee MM eeee-eeeeeee eeee eee eee eeeeeeeeee ee eee eeeeeee eee ee eeee-eeeeeeee eeeee. Meeeeeeeeeee, eee eeeeeeeeeee ee eeee ee eeeeee (8.8 eeeee) ee eeeeeeee eee eeeeeeee eeee eee eeeeeeee eee eeeeeeee eeeeeee.

Meeee 88 Meeeeeeeee Meeeeeeee Meeeeeee ee Meeeeeeee eee Meeeeee ee Meeeeeeeeeee[‌88‌‌88‌]

M8 M8 M8 M8 Meeeeeeeee eee ee
(%)
Meeee
(%)
Mee
Me Me M Me 88eee% 88, 8°M, eMeMM, 888e 88 88 [‌88‌]
Me Me M 8-eeeeeee 88eee% 88, 8°M, eMeMM, 888e 88 88 [‌88‌]
(MM8)8 M Me 88eee% 88, 8°M, eMeMM, 88e 88 88 [‌88‌]
Me M M Me 88eee% 88, 8°M, eMeMM, 88e 88:8 88 88 [‌88‌]
Me M M Me 88eee% 88 (M8=Me), 8°M, eMeMM, 88e 88:8 88 88 [‌88‌]
Me M M 8-M8MM8M8 88eee% 88, 8°M, eMeMM, 88e 88:8 88 88 [‌88‌]
Me M M 8-MeMM8M8 88eee% 88, 8°M, eMeMM, 88e 88:8 88 88 [‌88‌]
Me M M Me 88eee% 88 (M8=Me), 8°M, eMeMM, 88e 88:88 88 88 [‌88‌]
Me M M Me 88eee% 88 (M8=Me), 88°M, eMeMM, 88e 88:8 88 88 [‌88‌]
eMe M M Me 88eee% 88 (M8=Me), 88°M, eMeMM, 88e 88:8 88 88 [‌88‌]
Me M M Me 8eee% 88 (M8=Me),e ee,e M8M, 8e 88:8 >88 88 [‌88‌]
Me M M Me 8eee% 88 (M8=Me),e ee,e M8M, 88e 88:8 >88 88 [‌88‌]
Me M M Me 8eee% 88 (M8=Me),e ee,e M8M, 8.8e 88:8 >88 88 [‌88‌]
(MM8)8MM=MM8 M M Me 8eee% 88 (M8=Me),e ee,e M8M, 8e 88:8 >88 88 [‌88‌]
eMe M M (M)-MM=MMMe 88eee% 88 (M8=Me), 88°M, MeMM/M8M (8% e/e), 88e 88:8 >88 88 [‌88‌]
Me M M (M)-MM=MMMe 88eee% 88 (M8=Me), 88°M, MeMM/M8M (8% e/e), 88e 88:8 88 88 [‌88‌]
eMe M M (M)-MM=MMMe 8eee% 88 (M8=Me), 88°M, MeMM/M8M (8% e/e), 88e 88:8 88 88 [‌88‌]
Me M M Me 8.8eee% 88 (e=8), ee, eMeMM/MMMe8 (8:8), 88e 88:8 88 88 [‌88‌,‌88‌]
Me M M Me 8.8eee% 88 (e=8), ee, eMeMM/MMMe8 (8:8), 88e 88:8 88 88 [‌88‌,‌88‌]
eMe M M Me 8.8eee% 88 (e=8), ee, eMeMM/MMMe8 (8:8), 88e 88:8 88 88 [‌88‌,‌88‌]
Me M M 8-M8MM8M8 8.8eee% 88 (e=8), ee, eMeMM/MMMe8 (8:8), 88e 88:8 88 88 [‌88‌,‌88‌]
M (MM8)8 Me 88eee% 88, 8°M, eMeMM, 88e 88:8 88 88 [‌88‌]
M (MM8)8 8-Mee 88eee% 88, 8°M, eMeMM, 88e 88:8 88 88 [‌88‌]
M (MM8)8 8-MeMM8M8 88eee% 88, 8°M, eMeMM, 88e 88:8 88 88 [‌88‌]
M (MM8)8 8-MeM8M8 88eee% 88, 8°M, eMeMM, 88e 88:8 88 88 [‌88‌]
M (MM8)8M(MM8)8 Me 88eee% 88, 8°M, eMeMM, 88e 88:8 88 88 [‌88‌]
M (MM8)8M(MM8)8 Me 8°M, eMeMM, 88e 88:8 88 88 [‌88‌]
Me M Me Me 88eee% 88, 8°M, eMeMM, 88e 88:8 88 88 [‌88‌]
M M MM8MMMMMM Me 88eee% 88, 8°M, eMeMM, 88e 88:8 88 88 [‌88‌]

e Meeee (eee/eeee).

e Me eee eeeeeeee ee 88eee% ee MeMM.

e Meeeeeeee eeee eeee ee 8°M eee 8e, eeee ee ee eee eee eeeeeeeee eeee.

Me eee eeeee eeee, eeeeeeee 88 eee ee eeee ee eeeeeeee eeeeeee [eeee eee eee eeeeeeee eee 88 (M8=Me) ee 88 (e=8, 8)].[‌88‌] Mee eeeeeeee ee e eeeeee ee eee-eeeeeeee eeeeee eeeeeee eee ee eeeeeeee ee 8°M eeee ee ee 88% ee, eee eeee eeeeeeeee eeee eeee eeee eeeeeeee eeee eeeeeee eeeeeee. Meee eee eeeeeee ee eee eeeeeee eeeeeeee ee eeeeeee eeeee eeeee eeeeeeeeeee-eeeeeeee eeeeeeeee 88[‌88‌] eeee eeeeeeee eee eee ee 8eee% ee 8,8-eeeeeeeeeeeeeeeeeeeeee eeee ee ee-eeeeeeee, eeee eeeeeeeee eee eee ee eeeeeee eeeeee eeeeeeeeee.

M eeeeeeeee eeeeeeee eeeeeeee eee eeeee eeeeeeeee eee eeee eeeeeeeee, eeeee eee ee eeeeeee ee eee eeeeeeeee eeeeeeeee ee γ-eeeee eeeeeee. Meeee eee eeeeeeeeeee M,M-eeeeeeeeeeeeeeeee-8-eeeee eeeeee (88eee%) ee eeeee ee eeee eeeeeeeeeee, eee eeeeeeee ee eeeeeeeeeeeee ee (M)-β-eeeeeeeeeeee [(M)-(8-eeeeeeeeee)eeeeeee] eeeeeee eee Meeeeee eeeeeee eeee 88% eeeeeeeeee eee 88% ee ee 88eeeee (Meeeee 88). Mee eeeee eeeeeee eee eeeeeeee ee e eeeeee eeeeeeeeeeeeeeeee ee eeeeee eeeeeeeeeeeeeeee eeee eeeeeeee (>88% ee) eee ee e eeeeee eeeeeeeeeeee ee 88% eeeee.[‌88‌]

Meeeee 88 Meeeeeeee Meeeeeeee Meeeeeeee ee e γ-Meeee Meeeee ee Meeeeeeeee Meeeeeeee Meeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeee Meeeeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

Me eee eeeeeeeeeee eeeeeeeee, e eeee ee eee eeeeeeee eeeeeee (β-eeee eeeee ee eeeeeeeeeee) (8.8eeee) eee eee eeeeee eeeeeeee (88, M8=M ee Me; 8.888.88eeee) ee MMM (8.8eM) eee eeeee ee eee eeeee eeeeeee (8.8 ee 8.8eeee). Mee eeeeeeeee eeeeeee eee eeee ee eee eeeeeeeee eeeeeeeeeee eeeee eee eeeeeeee eeeeeee eee eeeeeeee. Mee eeeeeee eee eeee eeeeee eeeeeee e eeee (eeeeee eee) eee eeeeeee ee eee eeeeeeee. Mee eeee eee eeeeee eeee Me8M ee MeMMe (88eM). Mee eeeeeeee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeeee ee eeeeeeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee); eeeee: 8888%; 8888% ee.

8,8-Meeeeeee-8-eeeee-8-eeeeeeeeeeeee (88, M8=M8=Me; M8=M; M8=Me); Meeeeee Meeeeeeee:[‌88‌]

Meeeeeee 88 (88ee, 8.888eeee) eee eeeee ee e eeee eeeeeeeeee eeeeeeeeeeeeeeee (8-eeeeeeeeeeeeee; 8.88eM, 8.88eeee) eee eee eMeMM (8eM) ee 8°M. Mee eeeeeee eee eeeeeeeeee eeeeeee eee 88eee, eeee (M)-β-eeeeeeeeeeee [(M)-(8-eeeeeeeeee)eeeeeee; 88ee, 8.888eeee] eee eeeee. Mee eeeeeee eee eeeeeee eee 888e eeeee eeeeeeeeee ee eee eeeeeeee (MMM). Mee eeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeeeee eeeeeee eee eeee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 8:88 ee 8:8) eee eeeeeeeee eeee eeeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeeee e eeeee eee; eeeee: 88ee (88%); 88% ee.

References


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