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
1.3.1.1 Methyllithium

DOI: 10.1055/sos-SD-212-00234

Goldfuss, B.Science of Synthesis: C-1 Building Blocks in Organic Synthesis, (20141416.

Due to its highly polar C—Li unit,[‌2‌] methyllithium forms aggregates and provides, depending on its state of aggregation, highly nucleophilic (and also very basic) methylide equivalents. The high reactivity of methyllithium in additions to aldehydes or ketones is therefore hard to control, even at low temperatures. Stereoselective versions of such aldehyde or ketone methylations are thus difficult to establish. The polarity of the C—Li unit, however, also provides a solution for the selectivity problem. The affinity of methyllithium toward aggregation with neutral or metalated ligands leads to chiral complexes or chiral hetero-aggregates.[‌3‌,‌4‌]

Meee eeeeeeeeeee eeeeeeeeeeeee eeeeeeeee eeeeeeee eeeeeeeee eeeeeeeee eeee eeee eeeeeeee eeeeeeeeeeeeeeeeeee, eeee ee eeeeee eeeeeee eee ee eeeee eeeeeeeeeeee. M eeeeeee eeeeeeeee eee eeee eeeeeeee ee Meeeeeeee eee ee-eeeeeee, eeeeeeeee (−)-M-[(eeeeeeeeeeeeeee-8-ee)eeeeee]eeeeeeeeeee (8) ee eeeeee eeeeee ee eeeeee eeeeee, eeeeeeee 88% eeeeeee eeeeee ee eee eeeeeeeeeee ee eeeeeeeeeeee (Meeeee 8).[‌8‌]

Meeeee 8 Mee ee Meeeeeeeeʼe Meeeeeeeeeeee Meeeeee[‌8‌]

Mee eeee eeeee eeeeeeeee eeeeeee eeee eeeeeee eeeeee-eeeeeeeeee eeee eeeeeeeeeeeeee. Meeeee, eeeeeee 8-(eeeeeeeeeeeee)-8,8-eeeeeeeeeeeeeeeeee (8) eeeeeee ee ee 88% ee ee eee eeeeeeee ee eeeeeeeeeeeee ee eeeeeeeeeeee (Meeeee 8).[‌8‌] M eeeeeee eeeeee ee eeeeeeeeeeeee eee e eeeeeeee eeeeee ee eee eeeeee eeeeeee eeeeeeee 8 eee eeeee ee ee eeeeeee eee eee eeeeeeeeeee ee eee eeeeeeeeeee.

Meeeee 8 Mee ee Meʼe Meeeeeeeeeeee Meeeeeeee[‌8‌]

Meeeeeeeeee 8

Meeeeeeeeeeee (M) ee (%) Mee
8 MeMe MeMMM
8.88 8.88 8.88 88 [‌8‌]
8.88 8.88 8.88 88 [‌8‌]
8.88 8.88 8.88 88 [‌8‌]
8.88 8.88 8.88 88 [‌8‌]
8.88 8.88 8.88 88 [‌8‌]

Mee eeeeeeeee eeeeeeeeeee ee eeeeeeeeeeeee eeeee eeee eeeeeeeee eeeee eeee 88% ee.[‌8‌] Mee eeeeeee eeee eeeee eeee eee eeeeeeee ee eeeeeee eeeeeeee ee eeeeeee eeeeeeeeeee eeeeeeeee eee eeeeeeeeeeeeeeeeee ee eee eeeeeeeeeee eeeeeeee, ee eeeeeeeeeee eeeee ee eeeeeeeeeeee ee eee eeeeeeeee ee eeeeeeeee, eeeeeee eeeeeeeeee ee eeeeeeeeeeeee eee eee eeeeeeeee eeeee.[‌8‌]

Meeeeeee eee ee-eeeeeee eeee eeee eeeeeee eeeeeeeeee eeeeeeeeeeeeee ee eeeeeee eeeeeeee ee eeeeeeeeeeeee ee eeeeeeeee.[‌8‌] Meee, eeeeeeeee eeeeeee 8 ee eeeeeeeee ee eeeeeee eeeee eee, ee −88 °M, 8 eeeeeeeeee ee eeeeeeeeeeeee ee eeeeeee eeeee ee eeeee. Mee eeeeeeeee eeeeeeee ee eeee ee −88 °M eee 8 eeee eee eeee eee eeeeeeee ee eeeee ee eee eeeeeeeeeeeeeeee eeeeeeee ee −88 °M eeee e eeeeee ee 8 eeeee (Meeeee 8).[‌8‌]

Meeeee 8 Meeeeeeeʼe Meeeeeeeee Meeeeee ee Meeeeeee ee Meeeeeeeeeeee[‌8‌]

Meeeeeeeeee 8

M8 Meeee ee MeMe ee (%) Meeee (%) Mee
Me 8 88 88 [‌8‌]
Me 8 88 88 [‌8‌]
8-eeeeeeee 8 88 88 [‌8‌]
8-eeeeeeee 8 88 88 [‌8‌]
8-eeeee 8 88 88 [‌8‌]
8-eeeee 8 88 88 [‌8‌]
8-MeM8M8 8 88 88 [‌8‌]
8-MeM8M8 8 88 88 [‌8‌]
8-Mee 8 88 88 [‌8‌]

Meeeeeeeeeeeeeeeee eeeeeeeee eeee eeeeeeeeee eeeee eeeeee eeee eee eeeeeee eeeee ee eeeeeee 8 ee eeeeeee eeee eeeeeeeee eeeeeee eeeeeee ee eeeeeeeee. M eeeeee eeeeeeeeee ee eeeeeeeeeeeee eeeee eeee ee e eeeeee eeeeeeee ee eeee eeeee eee eeeeeeeeeeee eeeeee. Meee eeeee eeeeeeeeeeee, e eeeeeeeeeeee ee eeeeeeeeeeeee ee eee eeeeee eeeeeeeeee eeeeeee eee eeeeeeeee.[‌8‌] Meeeeee eeeeeeeeeeee ee eeeeeeeeeeeee eeee eeeee eeeee eeee (e.e., Me) eee eeeeeeeee ee eeee ee eee eeeeeeeee eeeeeeee.

Meeeeeeeee eee ee-eeeeeee eeee eeeeeeee eeeeee eeeee eeeeeeee 8 eee eeeeeeee ee eeeeeeeeeeeee ee eeeeeeeee eeeeee eeeeeeee eeee ee ee 88% ee (Meeeee 8).[‌8‌]

Meeeee 8 Mee ee Meeeeeeeeeʼe Meeee Meeeeeee[‌8‌]

Meeeeeeeeee 8

M8 M8 Meeeee ee 8 Meee (°M) Meeeeeeeee (%) ee (%) Mee
Me Me M −88 88 88 (M) [‌8‌]
Me Me M −888 88 88 (M) [‌8‌]
Me Me M −88 88 88 (M) [‌8‌]
Me Me M −888 88 88 (M) [‌8‌]
Me Me M −88 88 88 (M) [‌8‌]
Me Me M −88 88 88 (M) [‌8‌]
Me Me M −888 88 88 (M) [‌8‌]
eMe Me M −88 88 88 (M) [‌8‌]
eMe Me M −888 88 88 (M) [‌8‌]
eMe Me M −888 88 88 (M) [‌8‌]

Meeeeeeee eee ee-eeeeeee eeee eeeeeeee eeeeee eeeeeee eeeee 8 eee eee eeeeeeeeeee ee 8-eeeeeeeeeeeeeeeeee eeee 88% ee eeeee e 8:8:8 eeeee ee eeeeeeee/eeeeeeeeeeeee/eeeeee eeeeeee eeeee (Meeeee 8).[‌8‌]

Meeeee 8 Mee ee Meeeeeeeeʼe Meeeeeeeeeeee Meeeee[‌8‌]

Meeeeeee ee eeeeee eeeee eeeeeeeeee ee eeeeeeeee, eee eeee eeee eeeeeeeeee eeeeeeee ee eeee eeeeeeeeeeeeee ee eeeeeeeee ee eeeeeee eeeee eeeeeeeee eeeeeeeeee eeee eeeeeeeeeeeeeeeee eeeeeee ee eeeeee eeeeeeeee eeee ee eeeeeee. Meee e eeeeee eeeeeeeeee, eeeeeeee ee eee eeeeeeeeee eeeeeeeeeeeee eeeeeeeee, ee eee eeeeee eeeeeeeeeeeee eeeeeeeee eeeee eeeeee eeeeeeeee eeeeeeeeeeeeeeeee eeeeeeeeeeee ee eee eeeeee eeeeeeeee.[‌8‌] Me eee eeeee eeee eeeeeee eee eeeeeeeeeee eeeee ee Meeeee 8 eeee e eeeeee eeeeee ee eeeeeeeeeeeee [e.e., eeeeeeee/MeMe/eeeee (8:8.8:8.8)] eeee eee eeeee eee eeeeeeeeeee. Meeee, eee eeeeee eeeeeeeee 8 ee eeeeeeeeeeeee eee eee eeeee eeeeeeee eee eeeeeee eeeeee eeeeeeeeee eeeeee eee eeeeeeee eeeeeeee ee eeee eeeeeeeeeeeee ee eeeeee.[‌8‌] Meeeeee, eeeeee eee eeeeeeee, eee eeeeeeee eeeeeee ee eeeeeee eee eeeeeeeee ee eee eeeeeeeeeee eeee eee eeeeee eeeeeeee ee eeee eeeee eeeeeee eeeeeeeeee. Meee eeeee eeeeeeeeeeeeee eeeeeee ee eeeeee eeeeeeeee eeeeeeee eeeeeeeee ee eeeee eeeeeeeeeee eeeeeeeeeeee eeeeeeee. Meee eeeeeeeeee ee eeeeeeeeeeeee eeee eeeeeeee eeeeeeee eee eeee eeeeeee eee eeeeee ee eeeeeeeeeeeeeeeeee (eeee, ee. 88% ee). Meeeee, eeeeeee eeeeeee ee e eeeeee eeeeeeee, e.e. e eeeee ee eeeeeeee/eeeeeeeeeeeee/eeeee ee 8:8:8.88, eeeeeeee eee eeeeeeeeeeee eeeeee ee eee eeeeeeeeeee eeeee ee Meeeee 8 ee 88% ee.[‌8‌]

Meeeeeeee eee ee-eeeeeee eeee eeeeeeeee ee eee ee e eeeeeeeeeeeeeeeee eeeeeee ee eee eeeeeeeeeeeee eeeeeeee eee eeeee eeeee ee eeee e eee ee eeeeeeee eee eeeeeee eeeeeeee ee eeee ee eeeeee eee eeeeee ee eeeeeeeeee eeee eeeeee eee eeeeee eeeeeee eeeee ee eee eeeeeeeeeeee. Meee eeeeeee ee eeeeeeeee eeeeeee eeeeeeee ee eee eeeeeeee ee eeee eee eeeeeee eeeeeeee eeeeeee ee e eeeeee, eeeeeee eeeeeee eeeeeeee eeeeeeeee.[‌8‌] Meee, eeeee eeeeeee eee eeeee eeeeeeeee 8 ee eeeeeeeeeeeee eee eee eeeeee eeeeeee eeeee ee eeeeeeeeeeeeeee, 8 eeeeeeeeee ee eeeeeee eeeeeeee eee eeeee, eeeeeeee, eeeee 88 eeeeeee, ee 8-eeeeeeeeeeeeeeeeee. Meeeeee, eee eeeeeeeeeeeeeeeeee eeeeeeeee eeee 88 ee 88% ee, eeeeeeeeee eeee eeeeeee eeeeeeee eeeeeeee eeee eee eeeeee eeeee eeeeeeee. Me eeeeeee eeeeeeee eeeee ee eeee ee eeeeeeeeee eee eeeeeee eeeeeeee eeeeeee, eee eeeeee eeeeeee eeeee eeeee ee eee eeee eee eeeee ee eeeeeeee eeeeeeeeeeeeeeeeeeeee.[‌8‌]

Meeeeeeee eee ee-eeeeeee eeee eeeeee eeeee eee eeeeeee eeeeeeee eee eee eeeeeeee eeeeeeee ee eee eeeeeeeee eeeeeee eeeee/eeeeeeeeeeeee eeeeeeeee 8. Meee 8 eeeeeeeeee ee eeeeeee eeeee eee 8 eeeeeeeeee ee eeeeeee eeeeeeee, eee eeeeeeeeeee ee eee eeeeeeeeeeeee eeeeeeee eee ee eeeeeeee ee 88% ee. Meee eeee 8.88 eeeeeeeeeee ee eeeeeee eeeeeeee, e 8:8 eeeeeeeee ee eeeeeee eeeeeeee eee eeeeeee eeeeeeee eeeee; ee eeee eeee, 88% ee ee eeeeeeee. Meeee e eeeeeeeeeeeeeeeee eeeeee ee 8.88 eeeeeeeeeee ee eee eeeeee eeeeeee eeeee eeeeee ee ee eeeeeeeeee, eeee e eeeeee ee 88% ee (Meeeee 8).[‌8‌]

Meeeee 8 Meeeeeeeeʼe Meeeeeeeeeeeeeeee Meeeeeeeeeeee Meeeeeee[‌8‌]

References


Cookie-Einstellungen