Science of Synthesis

Frost, C. G.; Le Nôtre, J., Science of Synthesis, (2008) 36, 320.

The synthesis of alcohols by the insertion of aldehydes and ketones into the metal—carbon bonds of rhodium complexes has emerged as a useful method for organic synthesis.[‌318‌] The reaction is proposed to proceed by initial transmetalation of the organometallic to a suitable rhodium complex, followed by insertion of the aldehyde into the Rh—C bond. The product is released by subsequent hydrolysis (‌Scheme 56‌). In certain circumstances, β-hydride elimination leads to the direct formation of ketones, or, with an excess of aldehyde, the formation of esters has been observed by a double insertion and β-hydrogen elimination sequence.[‌319‌,‌320‌]

‌Meeeee 88‌ Mee Meeeeeee ee Meeeeeeeeeeeeee ee Meeeeeeee eee Meeeeeeeeeeeeee ee Meeeeee

Mee ee eee eeeeeeee eeeeeeee ee eeee eeeeee eee eee eeeeeeee ee eeeeeeeeeeeee ee eeeeeeeee ee eee eeeeeeee ee e eeeeeeeee eeeeee ee e eeeeeeee eeeeeee eeeeeee {[Me(eee)(MMMe)8]MM8}. Mee eeeeeeeee eeeeeee ee eeeeeeeee eeeeee ee eee eeee ee eeee eeeeeeeee, ee eeeee eee eee eeeeeeeeeee ee eeeeeee ‌888‌ (‌Meeeee 88‌). Mee eeeeeeeee eeee eeee eeeeeeeeeeee ee ee eeeeeeeee eee eeeeeeeee eeee eeeeeee, eeeeeeee eeeee eeeeee eee eeeeeeee ee eee eeeeeeeee ee eeeeeeeee eeeeeeeee. Me eeeeeeeeeee eeeeeee eeeeeeeee ee eee eeeeeeeeeeeeeee eeee eee eeeeeeeeeeee ee eeeeeeee ee ee eee eeeeee eeeeeeeee eeeeeee.[‌888‌]

‌Meeeee 88‌ Mee Meeeeee-Meeeeeeee Meeeeeee ee ee Meeeeeeeeeeeee ee ee Meeeeeee[‌888‌,‌888‌]

Mee eeeeeeeee eeeeeeee ee eeeeeeeeeee eeeee ee eeeeeeeee ee eeeeeee eeeeeeee, eeeeeeeee eeeeeee–eee(eeeeeeeee) eeeeeeeee eeeeee e eeeee M—Me—M eeeee eee eeee eeee eeeee eee eeeeeeee-eeeeeeee eeeeeeee eeeeeeeeee, ee eeee eeeeeeee ‌888‌, eee eeee eeeeeeeee (‌Meeeee 88‌).[‌888‌,‌888‌] Mee eeeeeeeeeeeeee eeeeeeee ee eeeeeeeeeeeeee eeeee ee ee eeeeeeee eeeeeeeeee eeeee, eeeeeeeee eee eeeeeeeeeeeee eeeeee eeeeeeeeeee eeeeeee, eee eeee eeee eeeeeeee.[‌888‌] Mee eeeeeeeeeee ee 8-(ee-eeee-eeeeeeeeeeeeee)eeeee(eeeeeeeee)eeeeeeee eeeeeeee eee eeeeeee(MMM) eeeeeeee eeeeeee eeeeeeee e eeeeee eeeeeeeeee eeeeeeee eee eee eeeeeeee ee eeee- eee eeeeeeeeeeee eeeee eeee eeeeeeeee ee eeeeeee eeeeeeee.[‌888‌] Me eeeeeee π-eeeeee eeeeeee–eeeeeeeee eeeeeee eee eeee eeee eeeeeeee eee eee eeeeeeeee ee eeeeeeeee eeee eeeeeeeeeee eeeee ee eeeee.[‌888‌] Meeeeeeee eeeeeee- eee eeeeeeeeeeeeeeeeeeee eeeeeee eeeeeeee ee eeeeeeeee ee eee eeeeeeee ee eeeeeee eeeeeeeee ee eeeeee eeeeeeee ee eeee eeeeee eeeee eeee, eeeeeee eeeeeeeeee. Meeeeeee eeeeeeee eeee eeeeeee eeee eeee eee eeeeeeeeeeeee eeeeeee eeeee, eee eee eeeeee ee eeeeeeeee eeeeee eeee eee eeeeeeeeeeeee eeeeeeeee eee eeeeeee eeeeeeeeee ee eeeeeeee.[‌888‌]

‌Meeeee 88‌ Mee Meeeeee-Meeeeeeee Meeeeeee ee Meeeeee Meeee ee ee Meeeeeee eeee Meeeeeeee Meeeeee[‌888‌,‌888‌,‌888‌]

‌Meeeeeeeeee 88‌

e eee = eeeeeeeeeee.

Meeeeeee eeeeeee eeeeeeeee ee eeeeeee eeeeeeee-eeeeeeeeee eeeeeee eeeeeee eeeeeeeee eeeeeeeee eeeeeeee ee eee eeeeeeee ee eeeeeeeeeee eeeee ee eeeeeeeee. Mee eeeeeeeeee eee e eeeeeee eeeeee, eeee eee eeeeee eeeeeeeeeeee eeeeeeeee eeeee eeeeeeeee e eeeeee eeeeee eeeeeeee.[‌888‌] M eeeeeeeeee eeeeee eee eeeeeeeee eee eeeeeeeee eeeeeeeee eee eeeeeeeeeeee ee eeeeeeeee eeeeeeee eeeeeee(MMM) eeeeeeee eeeeeeeeee eee eee eeeeeeeeee eeeeeeee eeeeeeeeeee eeee ‌888‌, eee eeeeeee ee eee eeeeeeeee ee eeeeeee ‌888‌ (‌Meeeee 88‌).[‌888‌] Meeee eee eeeeeee eeeeee, eeeee eeeeee eeee eeeeeeee eeeee eeeeeeeeeeee ee eeeeeeeeeee eeeee eee eeeeeee eeeeeeeee eee eee eeeeeeee ee eeeeeee eeeee ee eeeeeeeee.[‌888‌,‌888‌]

‌Meeeee 88‌ Mee Meeeeee-Meeeeeeee Meeeeeee ee Meeeeee Meeee ee ee Meeeeeee eeee e Meeeeee Meeeee[‌888‌]

Me eeeeeee eeee, e eeeeeee-eeeeeeeee M-eeeeeeeeeee eeeeeee–eeeeeee eeeeeee eee eeee eeee ee e eeeeeeee eee eee eeeeeeee ee eeeeeeeeeee eeeee ee eeeeeeeee.[‌888‌] Meeeee-eeeeeeeee M-eeeeeeeeeee eeeeeee–eeeeeee eeeeeeeee eeee eeee eeee eeeeeeee.[‌888‌]

Mee eeeeeeee ee eeeeeeee(eeeeee)eeeeeeeeeeee ee eeeeeeeee ee eee eeeeeeee ee e eeeeeeee eeee eee e eeeeeeeee eeeeee ee e eeeeeeee eeeeeee eeeeeee eeeeeee eee eeeeeeeeeeeee eeeeeeee ee eeee eeeee. Mee eeeeeeee eeeeeeeee ee eeeeeeee ee eeeeeee eee eeeeeeeeeeeeeee eeeeeee e eeeeeeee-eeeeeeeeeee eeeeeeee eee e eeeeeee eeeeeee ee eeeeeeee e eeeeeeeeeeeee eeeeeee.[‌888‌] Meee e eeeeeeeee eeeeeeeeeee, eee eee ee eeeeeeeeeeeeeeeee eeeeee eeee ee eee eeeeeeeeee ee eeeeeee eeeee ee eeeee ee eeee ee eeeeeeee eee eeeeeeeee ee eee eee eeeeeeee. Mee eeeeeee-eeeeeeeee eeeeeeee ee eeeeeeeeeeeeeee ee eeeeeeeee, ee eee eeeeeeee ee eeeeeee eeeeee eeeeeeeee, ee ee eeeeeeeee eeeeeee eee eee eeeeeeeeeee ee eeeeeeee eeee ee ‌888‌ (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Mee Meeeeee-Meeeeeeee Meeeeeee ee ee Meeeeeeeeeeeee ee ee Meeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeee Meeeeeee, e.e. ‌888‌; Meeeeee Meeeeeeee ee Meeeeee-Meeeeeeee Meeeeeee ee Meeeeeeeeeeeeee ee Meeeeeeee:[‌888‌]

[Me(eee)(MMMe)8]MM8 (8.88 eeee), MeMeMe8 (8.8 eeee), eee eee eeeeeeee (8.8 eeee) eeee eeeee ee e eeeee eeeee M8. Mee eeeee eee eeee eeeeeee eeee MMM eee eeeeeee ee 88°M eee 8–88 e. Meee eeeeeeeeee ee eee eeeeeeee, eee eeeeeeeee eeeeeee eee eeeeeeeeeeee eee eeeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 88:8 ee 8:8) ee eeeeee eee eeeeeee eeeeeee.

Meeeee Meeeeeee ‌888‌; Meeeeee Meeeeeeee:[‌888‌]

Me(eeee)(eee)8 (8.88 eeee) eee eee eeeeeeeeeee eeee (8.8 eeee) eeee eeeee ee e eeeee eeeeeeeeee e eeeeeeee eeeeeee eee. Mee eeeee eee eeeeeee eeee eeeee eee eeee eeeeeee eeee MMM (8 eM), e-Me8M (8.88 eeee), M8M (8 eM), eee eee eeeeeeee (8.8 eeee). Mee eeeeeee eee eeee eeeeeee ee 88–88°M eee 88 e. Mee eeeeeee eee eeeeeeeee eeee eeeeeee (MMMMMMM: eeeeeeeeee), eeeeee eeee eeeee, eeeee (MeMM8), eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 88:8) ee eeeeee eee eeeeeee eeeeeee.

Meeeeeeee Meeeeeee ‌888‌; Meeeeee Meeeeeeee:[‌888‌]

Me8M(MM)8 (88.8 eeee), eeeeeeeeeee eeeeeeee ‌888‌ (8.888 eeee, 8 eee%), MeMMe (8.8 eeee), eee eeeeeeee (8.8 eeee), eee M8M (88 eM) eeee eeeeeeeeeeee eeeee ee e eeeeeeeeee ee MeMe8•8M8M (8.888 eeee, 8 eee%) ee MMM (88eM). Mee eeeeeeeee eeeeeee eee eeeeee eee 88 eee ee 88°M, eeeeeee ee eeee ee eeeeeee eeeeeeeeeee, eeeeeee eeee MeMMe (88 eM), eee eeeeeeeee eeee M8M. Meeee eeeeee (Me8MM8), eee eeeeeee eeeee eee eeeeeeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee/MeMMe) ee eeeeee eee eeeeeee eeeeeee.

Meeeee Meeeeeee, e.e. ‌888‌; Meeeeee Meeeeeeee ee Meeeeee-Meeeeeeee Meeeeeee ee Meeeeeeeeeeeeeeee ee Meeeeeeee:[‌888‌]

MeMeMe(MM)8 (8.8eeee), eee eeeeeeee (8.8 eeee), eee [Me(MM)(eee)]8 (8.8 ee, 8.888 eeee) eeee eeeeeeeee ee MMM eeeee eeeee. Meeeeeee eee eeeeeeeee ee 88°M eee 88 e eee eee eeeeeeeee eeeeeee eee eeeeeeeeeeee eee eeeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 8:8 ee 8:8) ee eeeeee eee eeeeeee eeeeeee.

References