Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via
10.3.2.4 Oxidative α-C—N Coupling

DOI: 10.1055/sos-SD-225-00320

Uyanik, M.; Ishihara, K.Science of Synthesis: Catalytic Oxidation in Organic Synthesis, (20171661.

A highly efficient α-amination of aldehydes with amines is catalyzed by hypoiodite species (Scheme 30).[‌77‌] A catalytic amount of molecular iodine is used with sodium percarbonate as the oxidant. The reaction tolerates a wide range of functionalities, such as benzyl, allyl, or ester groups, as well as bulky aldehydes and secondary amine derivatives. Methanol is required as a co-solvent and the corresponding α-amino acetals 66 are obtained in good yields. Notably, no α-aminoaldehyde is detected, and only α-iodoaldehyde is isolated in the absence of methanol. Diastereoselective α-amination of 4-hydroxyalkanals affords the corresponding syn-2-amino-4–hydroxyalkanal dimethyl acetals in good yields and reasonable diastereoselectivities.[‌78‌]

Meeeee 88 Meeeeeeeee-Meeeeeeee Meeeeeeee α-Meeeeeeee ee Meeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 Meeee (%) Mee
(MM8)8 Me 88 [‌88‌]
Me M Me 88 [‌88‌]
8-eeeeeee M Me 88 [‌88‌]
Me M MM8MM=MM8 88 [‌88‌]
Me M MM8MM8Me 88 [‌88‌]

Meeeee α-eeeeeeeee ee eeeeeee eeee eeeeeeeee eeeeee eeee eeee eeeeee-eeeee eeeeeeeee (Meeeee 88).[‌88‌‌88‌] M-Meeeeeeeeeeeeee eeeeeeeee eee α-eeeeeeeee ee eeeee eeee eeeeeee ee eee eeeeeeee ee eeee-eeeee eeeeeeeeeeeee ee ee eeeeeee ee eeee α-eeeee eeeeeee 88.[‌88‌] Mee eeeeeeee ee eeeeeeeeeeeee eeee eeeeeeeee eeeeee eeeeeee eee eeeeeeeeeeeee α-eeee eeeeee. Meeeeee eee eeeeeee eeee eeeeeee eee eeeeeeeee eeeeee ee eeee eee eeeeeeeeeeeee α-eeeee eeeeeee 88 eeeee e eeeeeeeee eeeeee ee eeeeeeee eeeeee ee eee eeeeeeee ee eeeeee eeeeeeeeeeee (ee eeee-eeeee eeeeeeeeeeeee) ee eee eeeeeee.[‌88‌] Mee eeeeeeeee eeeee ee, eeeeeee, eeeeeee ee α-eeeeeeeee eeeeeee. Me eee eeeee eeee, eeeeeeeeeeeeeeeeee eeeeee eeeeeeeee eee eeeeeeeee α-eeeeeeeee ee eeeeeee eee eeeeee eeee eeee-eeeee eeeeeeeeeeeee ee ee eeeeeee ee eeee α-eeeee eeeeeee, e.e. 88 (Meeeee 88).[‌88‌] M eeee eeeee ee eeeeeee ee eeee ee 8,8-eeeeeeeeee eeeeeeeee eee ee eeee eeee eeeeeee eeeeeeeee eeeeeeeeeee, eeeeeeeee, eee eeeeeeeeeeee ee eeeeee eee eeeeeeeeeeeee α-eeeee eeeeeeee eeeeeeeee ee eeee eeeeee. Meeeeee, eeee eeeeeeee eeeeeeee eeeee eeeeeeee eeeeeeeeee (888 °M).

Meeeee 88 Meeeeeeee α-Meeeeeeee ee Meeeeee Meeee Meeeee-Meeee Meeeeeeee[‌88‌,‌88‌]

Meeeeeeeeee 88

M8 M8 M8 M8 Meeeeeeeee Meeee
(%)
Mee
Me Me (MM8)8M(MM8)8 e-MeMMM (8 eeeee),
MMM (88 eee%), ee, 8 e
88 [‌88‌]
8-eeeeeee Me (MM8)8MMMe(MM8)8 e-MeMMM (8 eeeee),
MMM (88 eee%), ee, 8 e
88 [‌88‌]
8-eeeee Me Me Me e-MeMMM (8 eeeee),
MMM (88 eee%), ee, 8 e
88 [‌88‌]
Me Me (MM8)8M(MM8)8 Me8MM8•8.8M8M8 (8 eeeee),
MM8M (88 eee%), 88 °M, 88 e
88 [‌88‌]
Me 8-MeMM8M8 (MM8)8M(MM8)8 e-MeMMM (8 eeeee),
MM8M (88 eee%), 88 °M, 88 e
88 [‌88‌]
Me Me Me MM8MM=MM8 Me8MM8•8.8M8M8 (8 eeeee),
MM8M (88 eee%), 88 °M, 88 e
88 [‌88‌]
Me Me M e-Me Me8MM8•8.8M8M8 (8 eeeee),
MM8M (88 eee%), 88 °M, 88 e
88 [‌88‌]

Meeeee 88 Meeeeeeee α-Meeeeeeee ee Meeeeee Meeee Meeeeeeeeeeeeeeeee Meeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeee (%) Mee
Me M 88 [‌88‌]
eeeeeeeeeee M 88 [‌88‌]
8-eeeeeee M 88 [‌88‌]
Me Me 88 [‌88‌]

Meeeeeee eeeeeeeeee eeeeeee eeeeeeeeeeeeeeeeee eeeeee eeeeeeeee eeeeeeeeeeeeeee eeeeeeeee α-eeeeeeeee eeee eeee-eeeee eeeeeeeeeeeee ee eee eeeeeee ee eee eeeeeeee ee eeeeee eeeeeee ee e eeee eeeeeeee ee eeee α-eeeee eeeeee 88 (Meeeee 88).[‌88‌] Mee eeeeeeee ee e eeeeeee ee α-eeeeeeeeeeeee eee α-eeeeeeeeeeeeeee eeeeeeee eeeeeeeeee eeee eeeeeee eee eeeeeeeee eeeeee eeeeeee eee eeeeeeeeeeeee α-eeeee eeeeee 88 ee eeee ee eeeeeeee eeeeee. Mee eeeeeeee ee eeeeeeee ee eeeeeee eee α-eeeeeeeeee, eeeeeeeeeeeeeee, eee eeeeeeeeeeee eeeeeeeeeeee eeeeeeeee. Mee eeeeeee α-eeeeeeeeee eeeee eeeeeeee eee eeeeeeeeee eeeeeeeeeeeeeee eeeeeee. Mee eeeeeeeeeeeeeee eeeeeeee ee eeeeeeeeeeee eeeeeeeee eeeeeeee eeeeeeee, eeeee eeeeeeee ee eeeeeee eeeeeeeeee/eeeeeeeeeeeeeee/eeeeeeeeeeee eeeeeeeeeeee, ee eeee α-eeeee eeeeee 88 ee eeee eeeeeeee eeeee eeeeeee eeeeeeeee eeeeeeeeee (Meeeee 88).[‌88‌] Meeeeee, e eeee eeeeeeee ee eee eeeeeeee eee eeee eeeeeeeeeeeeee.

Meeeee 88 Meeeeeeeeeeeeee Meeeeeeee α-Meeeeeeee ee Meeeeeee Meeeeeeeee Meeee Meeeeeeeeeeeeeeeee Meeeee/eeee-Meeee Meeeeeeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 M8 Meeee (%) Mee
Me M 8-MeMM8M8 M 88 [‌88‌]
Me M Me Me 88 [‌88‌]
Me M Me MM8MM=MM8 88 [‌88‌]
e-Me M Me Me 88 [‌88‌]
(M)-MM8MM=MMMe M Me Me 88 [‌88‌]
Me MMMee Me Me 88 [‌88‌]
Me MMMMM Me Me 88 [‌88‌]
M (MM8)8M(MM8)8 88 [‌88‌]

Meeeee 88 Meeeeeeeeeeeeee Meeeeeeee α-Meeeeeeee ee Meeeeeee Meeeeeee ee α-Meeee Meeeee Meeee Meeeeeeeeeeeeeeeee Meeeee/eeee-Meeee Meeeeeeeeeeee[‌88‌]

α-Meeee eeeeeeee eeeeeeeee eee eeeeee eeeeeeeee eeeeeeeeeeeee eee eeeeeeeeeeee eeeeee eeeeeeeee eee eeeeeeeeee eeeeeee eeeeeeeee. Meeee eeeeeeeee eee eeeeeeeeeeeee eeeeeeee ee eeeeeeeeeeee eeeeeeeeeeee eeeeeeeee ee eeeeee eeeee eeee α-eeee eeeeeeee eeeeeeeee. M eeeeee eeeeeeeee ee 8,8-eeeeeeeeee eeeeeeeee eeee eeeeee eeeee eeeeeeee eeeeeeeeeee eeeee eeeeeee eeeeeeeeeeee ee eeeee eeeeeeeee eeeeee ee eeeeee eeeeee ee eee eeeeeeee ee 8-eeeeeeeeeeeee eeee eeeeeeeeee (MMM)-MM8M 88 ee eee eeeeeee (Meeeee 88).[‌88‌] M eeeeeee ee eeeeeeee 8-eeeee-8,8-eeeeeeeeee eeeeeeeee 88 eee eeeeeeee ee eeee eeeeee. Meeeeeeeeee, eee eeeeeeee ee 8-eeeeeeeeeeeee 8,8-eeeeeeeeee eeeeeeeee eeeeeee eee eeeeeeeeeeeee 8,8-eeeeeee eeeeeee 88 eeee eee eeee eeeeeeeee ee eeeeee eeeee eeeeeeeeeee eeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee 8-Meeeeeeee ee 8,8-Meeeeeeeee Meeeeeeee Meeee Meeeee Meeeee eee e 8-Meeeeeeeeeeee Meee Meee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 Meeee (%) Mee
Me Me MMe 88 [‌88‌]
eMe Me MMe 88 [‌88‌]
(MM8)8MM Me MMe 88 [‌88‌]
8-eeeee Me MMe 88 [‌88‌]
(MM8)8MM=MM8 Me MMe 88 [‌88‌]
Me (MM8)8M 88 [‌88‌]
MMe (MM8)8 88 [‌88‌]
MMe Me MMMe 88 [‌88‌]
(M)-MM=MMMe Me MMe8 88 [‌88‌]

Meeeee 88 Meeeeeeee 8,8-Meeeeeeeeee ee 8,8-Meeeeeeeee Meeeeeeee Meeee Meeeee Meeeee eee e 8-Meeeeeeeeeeee Meee Meee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeee (%) Mee
MMe MMe 88 [88]
Me MMe 88 [88]
MM8e-Me MMe 88 [88]
8-eeeeeee MMe 88 [88]

Meeeeeeeeeee Meeeeeeee

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

Me e eeeeeee ee Me8MM8•8.8M8M (88.8 ee, 8.8 eeee, 8 eeeee), Me8MM (88.8 ee, 8.8 eeee, 8.8 eeeee), eee eeeeeeeeeeeeeeeeee (88.8 ee, 8.88 eeee, 8.8 eeeee) ee MeMM (8.8 eM)/8,8-eeeeeeeeeeeeee (8.8 eM) eee eeeee M8 (88.8 ee, 8.8 eeee, 88 eee%) ee ee. Mee eeeeeee eee eeeeeee ee 88 °M eeeee Me8MM eee eeeeeeeeee eeeeeeeee (MMM eeeeeeeeee). Mee eeeeeeeee eeeeeee eee eeeee eeee e eeeee eeeeee ee eeeeee eee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe); eeeee: 888 ee (88%).

α-Meeee Meeeee 88; Meeeeee Meeeeeeee:[‌88‌]

Meeee (8.8 eeee, 8 eeeee), eeeeeee eeeeeeeeee (8.8 eeee, 8 eeeee), MeMMe (8 eeee, 8 eeeee), MMMM (8.8 eeee, 88 eee%), 88% ee e-MeMMM (8.8 eeee, 8.8 eeeee), MeMM (8.8 eM), eee M8M (8.8 eM) eeee eeeee ee e eeee eeee eeeee eee. Mee eeeeeeeee eeeeeee eee eeeeee ee ee eee eeee ee 88 °M eee 8 e. Mee eeeeeeee eee eeeeeeee ee eee eeeeeeee ee eee. Me8MM8 eeee. Mee eeeeeee eeeee eee eeeeeeeee eee eeeeeeeee eeee MeMMe. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee).

Meeee 8-Meeee-8-eeeeeeeeeeeeee-8-eeeeeeeeeee [88, M8 = MMe; M8,M8 = (MM8)8]; Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeee ee eeeee eeeeee eeee eeeee eeeeeeeee eee eeeeee eeeee eee eeeeeeeee eeeeeeeee eeee.

Me e eeee ee eeeee 8-eeeeeeeeeeeeee-8-eeeeeeeeeee (88.8 ee, 8.888 eeee, 8.8 eeeee) ee MMMM (8.8 eM) eee eeeee 8 M ee MeM8 (8.8 eM, 8.8 eeeee). Me eee eeeeeeeee eeeeeee eeee eeeee MeM (8.8 ee, 8.8888 eeee, 88 eee%) eee MMM-MM8M 88 (88.8 ee, 8.888 eeee, 8.8 eeeee). Mee eeeeeee eee eeeeeee eee 88 eee ee ee. Mee eeeeeeee eee eeeeeeee ee eeeeeeee ee eee. ee Me8M8M8 (88 eM). Mee eeeeeee eeeee eee eeeeeeeee eee eeeeeeeee eeee Me8M (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee eee eeeee (MeMM8). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe); eeeee: 88.8 ee (88%).

References


Cookie-Einstellungen