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1.9.1.8 Hydroformylation Using Phosphite Ligands

DOI: 10.1055/sos-SD-201-00223

van Leeuwen, P. W. N. M.Science of Synthesis: Stereoselective Synthesis, (20111428.

Bulky monophosphites are useful ligands for the relatively fast hydroformylation of otherwise unreactive alkenes such as cyclohexene and alkenes not sensitive toward double-bond isomerization. The rates obtained are several orders of magnitude higher than those obtained with triphenylphosphine.[‌12‌] For simple alk-1-enes such as oct-1-ene very high rates are also obtained using tris(2-tert-butylphenyl) phosphite, with turnover frequencies of up to 180000h1 (90°C, 20atm).[‌15‌] The explanation is that more bulky ligands favor the formation of mono-ligand rhodiumcarbonyl complexes, which are much more active catalysts than bis-ligand or tris-ligand complexes for both steric and electronic reasons. Unfortunately isomerization is also a fast reaction when these catalysts are applied. Therefore they are particularly attractive for alkenes that do not undergo isomerization of the double bond, such as limonene, or for alkenes in which isomerization is not productive, as in cyclohexene and propene. Related bulky monophosphites have also been reported and they work equally well; examples are tris(2-tert-butyl-4-methylphenyl) phosphite, tris(2-tert-butyl-4-methoxyphenyl) phosphite, and tris(2,4-di-tert-butylphenyl) phosphite. Until the introduction of bulky phosphites, terpenic alkenes were hydroformylated with catalytic triphenylphosphine complexes under rather drastic conditions [600atm, >120°C (BASF)].[‌90‌]

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Meeeee 88 Meeeeeeeeeeeeeee ee Meeeee 8-Meeeeeeeeeeeee[‌88‌]

Meeeeeeeeee 88

Meee (°M) Meeeeeee (eee) Meee (e) Meeee (88/88/88) Meeeeeeeee (%) Mee
88 88 88 88:88:8 88 [‌88‌]
888 88 88 88:8:88 88 [‌88‌]

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Meeeee 88 Meeeeeeeeeeeeeee ee Meeeeeeeeeeeee Meeeeeee Meeeeee eeee e MeeeeeeMeeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) Mee
(MM8)8Me 88 [‌88‌]
(MM8)8Me 88 [‌88‌]
(MM8)8MM8Me 88 [‌88‌]
(MM8)8MM8M 88 [‌88‌]
(MM8)8MM8Me 88 [‌88‌]
(MM8)8MMe8 88 [‌88‌]
(MM8)8MM 88 [‌88‌]
(MM8)8Me 88 [‌88‌]
(MM8)8M 88 [‌88‌]
(MM8)8MM 88 [‌88‌]
MM(MMe)8 88e [‌88‌]
MM8MM(MMe)8 88 [‌88‌]
88e [‌88‌]
88e [‌88‌]

e Meeeeee eeeee (eeeeee/eeeeeeee) 88:8.

e Meeeeee eeeee (eeeeee/eeeeeeee) 88:8.

e Meeeeee eeeee (eeeeee/eeeeeeee) 8.8:8.

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Meeeee 88 Meeeeeeeeeee ee Meeeeeeeeeee Meeeeeeee[‌88‌]

Meeeeeeeeee 88

Meeeeee Meeee (88/88) ee (%) ee 88 (Meeeee) Meeeeeeeee (%) ee Meeeeee Meeee (88/88) ee (%) ee 88 (Meeeee) Meeeeeeeee (%) ee Mee-8-eeeeeeeeee Meeee (88/88) ee (%) ee 88 (Meeeee) Meeeeeeeee (%) ee Meeee Meeeeee Mee
(M,M)-Meeeeeeeee 88.8:8 88 (M) 88 8.8:8 88 (M) 88 888:8 88 (M) 88 [‌88‌]
(M,M)-Meeeeeeeee 8.8:8 8 (M) 88 88.8:8 88 (M) 88 888:8 88 (M) 88 [‌88‌]
(M,M)-MMMMMMMM 8.8:8 88 (M) 88 8.8:8 88 (M) 88 8.8:8 88 (M) 88 [‌88‌]

e Meeee (Meeeee/Me) 8.8:8; eeeee (eeeee eeeee eeeeeeeee/Me) 88888:8.

Meeeeeeeeeee Meeeeeeee

8-(8-Meeeeeeeeeeeee-8-eeee)eeeeeee (88); Meeeeee Meeeeeeee:[‌88‌]

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eeee-Meeee 8,8-Meeeeeee-8-eeeeeeeeeeeee (88):[‌88‌]

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eeee-Meeee 8-eeeeeeeeeeeeee, Me(eeee)(MM)8 (8.88eee%), eee eeee(8,8-ee-eeee-eeeeeeeeeee) eeeeeeeee (8eee%) eeee eeeeeeeee ee eeeeeee eee eeeeeeeeeee ee e 888-eM eeeeeeeee eeeee eeeeeeeee. Mee eeeeeeee eee eeeeeee eee ee 88°M eeeee 88eee ee M8/MM (8:8). Meeee 88e, eee eeeeeeeeee eee 88%. Mee eeeee ee eeeeee ee eeeeeeee eeeeeeee (88/88) eee 8.8:8. Meeeeeeeee, eeeeee, eee eeeeeeeeeee eeee eeeeeeee ee MM eeeeeee eeeeeeee (88eee%) eeeee ee ee eeeeeeee eeeeeeee. Mee eeeeeeee ee eee eeeeeeee eee eee eeeeeee eeeeeeeeeeeee eeee eeeeeee eeeeeeeee ee 8MMMM eeeeeeeeeee eee MM- eee MM-MM.

8-Meeeeeeeeee [88, M8=(MM8)8Me]; Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Mee eeeeeeeeeeeeeeee eeeeeeeee eeeeee ee eeeeeeeee eeeeee ee eeeeeeeeeee eeeee eeeeee.

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee, eee eeeeeeee ee eeeeee eeeeeeeeeeeeee eee eeeeeee eeee ee e eeee.

Meee: eee eeeeeeeee eeeeeeee ee eeee eeee eeeeeeeee ee e MeeeeeeMeeeee eeeeee eeeeee e eeeee eeeeee, eee ee eeeeee ee Meeeeee 8.8.8.8 ee ee eeeeeeee eeeeeeeeeee ee eee eeeee eeeeeeeeee.

Me eee eeeeeee eeee eeeee Me(eeee)(MM)8 (88ee, 8.888eeee, 8.88eee%), Meeeeee (88; 888ee, 8.888eeee), MMM (88eM), eee eee-8-ee-8-eee (8.88eM, 88eeee). Mee eeeeeeee eeeeee eee eeeeeeee eeeee eeeee eee eeeeeee eeee eeeeee (MM/M8 8:8) eee eeeeeeeeee. Mee eeeeeeee eeeeee eee eeeeeeeeeee ee ee ee 8.8eee eeee eeeeee eee eeee eeeeee ee 88°M eee 88e. Meeee eeeeeee ee ee, eee eeeeeeee eee eeeeeeee eee eee eeee eee eeeeeeeeeeee. Mee eeeeeeeee eee eee eeeeeeee ee Meeeeeeee eeeeeeeeeeee ee eeee e eeeeeeeee eee; eeeee: 8.88e (88%). Meee: eeeeeee eeeeeeeeee ee eee eeeee eeeeeeeeee, eee eee eee ee eeeeeee ee eeeeeeeeeeee eee eeeeeee e eeeeee ee eeeee eeee eeeeee eee eeeeeeeee eee eeeeeeee eeeee eee eee eee eeeeeeeee ee eee eeeeee eee eeee eeeeeee ee ee eeeeeeeeee eee eeeee.

References


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