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
4.4.7.2.1.5 Copper-Catalyzed Silylation

DOI: 10.1055/sos-SD-104-00395

Delvos, L. B.; Oestreich, M.Science of Synthesis Knowledge Updates, (2017186.

The transmetalation of the Si—B bond with copper alkoxide complexes (see General Introduction) offers the possibility to selectively transfer the silyl group onto alkynes by silacupration to generate vinylic silanes after protolysis (for reactions with ynones, see Section 4.4.7.2.6.3). This strategy dates back to early work with silylborates[‌58‌] and has been significantly expanded in recent years by the introduction of [dimethyl(phenyl)silyl]pinacolborane (19) as silicon source.[‌59‌‌62‌]

Meeeee-eeeeeeeee eeeeeeeeee ee eeeeeeee eeeeeee 88 eeee eeeeeeeeeeeeee Me—M eeee eeeeeeeee ee eee eeeeeeee eeeeee eeee eeeeeeeee eeeeeeee eeeeeee eeeeeee 88 (Meeeee 88).[‌88‌] Mee eeeeeeeee eeeeeeeeee eee 88 eee% ee eeeeee(M) eeeeeeee eee eeeee eeeeeeeee eeeeee 88 eeeeeeee eeee 88 eee% ee eeeeee eeee-eeeeeeee eee eeeeee eeeeeeee ee eeeeee eeeeee. M eeeeeee ee eeeeeeeeee eeee eeeeeeeeeeeeee eee eee-eeeeeeeeeeeeee eeeee eeeeeeeeeeee eee eeeeeeeee eeee eee eeeeeeeeeeeee eeeeeee eeeeeee 88 ee eeee eeeeee. Me eeeee ee eeeeeeeeeee eeeeeee eeeeeeeeeee, eee ee ee eeee eeeeeeeeeeeeeee (88, M8 = Me) eeee eeeeee eeee eeeeeeeeeeeeee eeeeeeeeeeeeeeee.

Meeeee 88 Meeeeeeee ee Meeeeeee Meeeeee Meeeeee ee Meeeee-Meeeeeeee Meeeeeeeee ee Meeeeeee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (88/88) Meeeee (%) Mee
(MM8)8Me 88:8 88 [‌88‌]
(MM8)8Me 88:8 88 [‌88‌]
(MM8)8Me 88:8 88 [‌88‌]
(MM8)8MM 88:8 88 [‌88‌]
(MM8)8MM 88:8 88 [‌88‌]
(MM8)8MM8Me 88:8 88 [‌88‌]
MM8MMe8 88:8 88 [‌88‌]
88:8 88 [‌88‌]
eeeeeeeeeee 88:88 88 [‌88‌]
Me 88:88 88 [‌88‌]

e Meeeeeee eeeee ee eeee eeeeeeeeeeee.

Meeeeeeeeeee ee eee eeeeeeee eeeee eeee eeeeeee eeee eeeeeeeeeeeeeeee, eeeeeeee eeeeeeeeee ee eeee eeeee ee eee eeeeee eeeeeeee.[‌88‌,‌88‌] Meee, eeeeee eeeeeee eeeeeee 88 eee eeeeeeeeeee eeeeeeee eeee eeeeeee 88 eeeee eeeeee eeeeeeeee eeeeeeee eeeeeeeeee eeeee eeeeeeeeeeeee eeee 88 ee eeeeee eeeeeeeee (Meeeee 88).[‌88‌] Mee eeeeeeeee eeeee eeee eeee eeee 8.8 eee% ee eeeeee(M) eeeeeeee eee eee eeeeeeeeeeeeee eeeeeee eeeeeeeee 88, eeee eeeeeeeee eeeeee eeeeeeeeee. Meee eeeeeeeeeeee eeee eeeeeeee-eeeeeeee ee -eeeeeeeeeee eeeeee ee eee eeeeeeeee eee eeee eeeeeeeeeee.

Meeeee 88 Meeeeeeee ee Meeeee Meeeeee Meeeeee ee Meeeee-Meeeeeeee Meeeeeeeee ee Meeeeeee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) Mee
Me 88 [‌88‌]
(MM8)8Me 88 [‌88‌]
(MM8)8MM8Me 88 [‌88‌]
Me 88 [‌88‌]
Me 88 [‌88‌]
8-Mee 88 [‌88‌]
8-M8MM8M8 88 [‌88‌]
8-MeMM8M8 88 [‌88‌]
8-MM8M8 88 [‌88‌]
8-eeeeeee 88 [‌88‌]

Meeeeeee, eee eeeeee eeeeeeeeeee ee 8.8 eee% eeeeee(M) eeeeeee–eeeeeeee eeeeeee eeeeeee eee eeeeee eeeeee eeeeeeeee/eeeeeeee eeeeeeeee eee eeeeeeeee ee eeeeee eeeeeee eeeeeee eeeeeeee eeee eeeeeeee eeeeeee eee eeeeeeeeeeee eeeee 88.[‌88‌] Meee eeeeee eee eeeeeee eeee eeeeeeeeeeeee eee eeeeeeee eee e eeeee ee eeee-eeeeeeeeeee eeeeeee eee eee eeeeeeeeeeeeeeee eee eeeee-eeeeeeeeeee eeeeeeee eeeeeeee ee eeee eeeeeeeeee. Meeeeeeeeeee, eee eeeeeeeeee ee eeeeeeee eeeeeee 88 eeeeeee e (eee)eeee eee ee eeeee eeeeeeeeeee eee eeee eeeeeeee (Meeeee 88). 8,8-Meeeeeeeeeeee eeeeeee eeeeeee 88 eee eeeeeeeee eeee eeeeeeeeeeeee eeeeee eeeeeeeeeeeeeeee eee eeeeeeeee M/M eeeeee ee eeee eeeeee. Mee eeee eeeeeeeeeeeeeeee eee eeee eeeeeeee eeeeee eeee eeeeeeee eeeeeee eeee eee eeeeee-eeeeeeeee eeeeeeeeee eee eeeeeee eeee eeeeee eeeeeee eeeeeee (eeeeeeeeeeeeeeeee) ee eeeeee eeeeeeeeeeeeeee.[‌88‌]

Meeeee 88 Meeeee-Meeeeeeee Meeeeeeeeeeeee Meeeeeeeee ee Meeeeeee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeee (M/M) Meeee (88/88) Meeeee (%) Mee
8-M8MM8M8 Me >88:8 88:8 88 [‌88‌]
8-MMM8M8 Me >88:8 88:8 88 [‌88‌]
8-MMM8M8 Me >88:8 88:88 88 [‌88‌]
8-MMM8M8 Me >88:8 88:8 88 [‌88‌]
8-eeeeeee Me 88:8 >88:8 88e [‌88‌]
8-eeeeeeeee Me >88:8 88:8 88 [‌88‌]

e Meeee ee eeee eeeeeeeeeee.

e Meeeeeee eeeee ee eeee eeeeeeeeeeeee.

Mee eeeeeeeeeeee ee e eeeeeee-8-eeeeeeeeee eeeee ee eee eeeeeeeeeee eeeeeeee ee ee eeeeeeee eeeeee eeee eeeeee eee eeeeeeeeeee ee eeeeeee eeeeeeeeee ee eeeeee eeeeee eeeeee eeee.[‌88‌] Meeee eeeeeeeeeee eeeeeeee eeeeeeeeee eeeeeeee eeee eeeeeeeeeeeeeeeeeeeeee ee eeeeee, eee eeeeee-eeeeeeeee Me—M eeee eeeeeeeee eeeeee eeeeeeeeeeeee ee eee γ-eeeeeeee eeee eeeeeee ee eee eeeeeee-8-eeeeeeeeee eeeee ee 88, eeeeeeeeee eee eeeeeeeeeeeee eeeeeee eeeeeee 88 ee eeeeee eeeeee-eeee eeeeeee (Meeeee 88). Meeeeee eeeee eeeeeeeeeeee eee eeeeeeeee eeeee eeeeeeeee eeeeeeeeee eee, ee eeee eeeee, eee 88/88 eeeeee eeeeee eeeeeeeeeeeeee.

Meeeee 88 Meeeee-Meeeeeeee γ-Meeeeeeee Meeeeeeeee ee Meeeeeeeeee Meeeeee-8-eeeeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeee (88/88) Meeeee (%) Mee
Me M 88:8 88 [‌88‌]
eMe M 88:88 88 [‌88‌]
(MM8)8Me M 88:8 88 [‌88‌]
(MM8)8Me M 88:8 88 [‌88‌]
(MM8)8MM M 88:88 88 [‌88‌]
Me Me 88:8 88 [‌88‌]
eMe Me 88:8 88 [‌88‌]

e Meeeeeee eeeee ee eeee eeeeeeeeeeee.

Meeeeeeeeee eeeeeeee 88 eeeeeeeee ee eee eeeeeeee ee eeeeeeeeee eeeeeeeeeeeeeeeeee eeeeeeeee ee eeeeeeeee eeeeeeeeeeeee 88, eeeee eee ee eeeeeeeee eeeeeeee ee eeeeeeeee eeeeeeee eeeeeeeeee ee e eee-eee eeeeeeeee.[‌88‌] Me eeee eeee, eee eeeeeee-8-eeeeeeeeee eeeee eeeeeee eee eeeeeeeeee ee eee β-eeeeeeee, eeeeeeeee ee eeeeeeeee eeeeeeeee ee eeeeeee eeeeeee 88 ee e eeeeeee ee eeeee eeeeeeee (Meeeee 88). Me eeeeeeeeee ee eee γ-eeeeeeeeee eeeeeeee, eeeeee eee eeeeeee eeeee eee eeee eeeeeeee ee eeeeeeeee eeeeeeee eeeeee eeee eeeeeeeee.

Meeeee 88 Meeeee-Meeeeeeee β-Meeeeeeee Meeeeeeeee ee Meeeeeeeeee Meeeeee-8-eeeeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeee (%) Mee
Me Me 88 [‌88‌]
eMe (MM8)8Me 88 [‌88‌]
Me Me 88 [‌88‌]
Me MM8e-Me 88 [‌88‌]
(MM8)8MMMMMM (MM8)8Me 88 [‌88‌]
(MM8)8Me Me 88 [‌88‌]
(MM8)8MM Me 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeee(eee-8-ee-8-ee)(eeeeee)eeeeee [88, M8 = (MM8)8Me]; Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeeee, e eee 88-eM eeeee eeee eee eeeeeee eeee MeMe (8.8 ee, 88 µeee, 88 eee%), e-MeMMe (8.8 ee, 88 µeee, 88 eee%), eee eeeeeeeee eeeeee 88 (8.8 ee, 88 µeee, 88 eee%). Mee eeeeee eeee eeeee eeee MMM (8.8 eM) eee eee eeeeeee eee eeeeeee eee 88 eee. 8-[Meeeeeee(eeeeee)eeeee]-8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee (88; 88 ee, 8.88 eeee, 8.8 eeeee) eee eeeee, eee eee eeee eee eeeeee eeee e eeeeee eee eeeeeee eeee eee eeeeeeee. Mee eeeeeee eee eeeeee ee 8 °M eeeee M8 ee e eeeeeeeeee eee eeee eeeeeee eee eeeeeee eee 88 eee. Mee-8-eee [88, M8 = (MM8)8Me; 88 ee, 8.88 eeee, 8.8 eeeee] eee MeMM (88 µM, 8.88 eeee, 8.8 eeeee) eeee eeeeeeeeeeee eeeee ee eee eeee eee eeeeeee. Mee eeeeeee eee eeeeeeeeee ee 8 °M eee 88 e. Meee, eee eeee eee eeeeeee eeee MM8Me8, eeeeeeee eeeeeee Meeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee); eeeee: 88 ee (88%).

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

Me e eeeeeeee eeeee M8, ee eeee-eeeee eeee eeee e eeeeeeee eeeeeee eee eee eeeeeee eeee eeeeeeeeeeeee eeee 88 (88 ee, 88 μeee, 8.8 eee%), MeMe (8.8 ee, 88 μeee, 8.8 eee%), e-MeMMe (88.8 ee, 8.888 eeee, 8.88 eee%), eee MMM (88 eM). Mee eeeeeeee eeeeee eee eeeeee, eee eee eeee eee eeeeeee ee 88 °M eee 8 e. 8-[Meeeeeee(eeeeee)eeeee]-8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee (88; 8.88 e, 8.88 eeee, 8.88 eeeee) eee eeeee ee eee eeee, eeeeeee eee eeee ee eeee eeee eeeee eeeeeeeeeee. Mee eeee eee ee-eeeeee eee eeeeeee eeee eee eeeeeeee, eee eee eeee eee eeeeeee ee 88 °M eee 88 eee eeeee M8. Meeeeeeeeeeeeee (88, M8 = Me; 888 µM, 8.88 eeee, 8.88 eeeee) eee MeMM (888 µM, 88.8 eeee, 8.88 eeeee) eeee eeeee. Mee eeeeeeeee eeeeeee eee eeeeeeeeee ee 88 °M eee 88 e eeeeee eee eeeeeeee eee eeeeeeee ee eeeeeee eee eeeeeee eeeeeee e eeeee eeee ee Meeeee eee eeeeee eee, eeeeeee eeee Me8M (8 × 8 eM). Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeeee e eeeee eee, eeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeee/Me8M 88:8) ee eeeeee eee eeeeeee ee e eeeeeeeee eee; eeeee: 8.88 e (88%).

Meeeeee Meeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

M eeeee-eeeee Meeeeee eeee eee eeeeeeeeeeee eeeeeee eeee MeMe•MMe8 (8.8 eee%) eee Me8MM8 (8.8 eeeee). MM8Me8 (8.88 M) eee eeeee, eee eee eeeeeeeee eeeeeeeeee eee eeeeeeeeee ee ee eee 88 eee eee eeeeeeeeeeee eeeeee ee 8 °M. Me eeee eeeeeeeeeee, 8-[eeeeeeee­(eeee­ee)eeeee]-8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee (88; 8.8 eeeee) eee eeeee, eee eee eeeeeee eee eeeeeee eee eeeeeee 88 eee, eeeeeeee ee eeeeeeee ee MeMM (8.8 eeeee) eee eee eeeeeeeeeeeee eeeeee 88 (8.8 eeeee), eeeeee eeee ee eeeeeeeee ee MM8Me8 (8.88 M). Mee eeeeeee eee eeeeeee ee eeeeee eeee ee ee eee eeeeeeeeee ee eeee eeeeeeeeeee eeeee eeeeeeee ee ee eeeeeee ee MMM ee MMM eeeeeeeee eeeeeeee eeeeeeeeee ee eee eeeeee eeeeeeeee (8–88 e). Mee eeeeeee eee eeeeeeee eeeeeee e eeeee eee ee eeeeee eee eeeee e-MeMMe ee eeeeee. Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeeeee/MeMMe) ee eeeeee eee eeeeeeeeeeee eeee eeeeeeee ee eeeeeeeee eeee. Mee 88/88 eee M/M eeeeee eeee eeeeeeeeee ee MMM eee 8M MMM eeeeeeeeeeeee eeeeeeee eeeee ee eeeeeeeeeeee.

Meeeeee Meeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

Mee eeeeeeeeeeeee eeeeeeeeeee eeeeeee 88 (8.88 eeee, 8.8 eeeee) eee Me8M+ M8MM8 (88 ee, 8.88 eeee, 8.8 eeeee) eeee eeeeee ee e Meeeeee eeee. Mee Meeeeee eeee eee eeeeee eee eeeeeeeeee eeee eeeee, eee eeeee eeeeeee (8.8 eM) eee eeeee. Mee eeeeeee eee eeeeeee ee 88 °M eee 8 e. M eeeeeeee Meeeeee eeee eee eeeeeee eeee MeMe (8.8 ee, 88 μeee, 88 eee%). Meee Meeeeee eeee eee eeeeee eee eeeeeeeeee eeee eeeee. Meee, eeeee eeeeeee (8.8 eM), e 88-ee% eeee ee Me8M ee eeeeeee (88 μM, 88 μeee, 88 eee%), eee e 8.8 M eeee ee e-MeMMe ee MMM (88 μM, 88 μeee, 88 eee%) eeee eeeeeeeeeeee eeeee, eee eee eeeeeeeee eeee eee eeeeeee ee 88 °M eee 8 eee. 8-[Meeeeeee(eeeeee)eeeee]-8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee (88; 88 ee, 8.88 eeee, 8.8 eeeee) eee eeeee ee eee eeee, eeeeeee ee ee eeee eeee eeeee eeeeeeeeeee. Mee eeeeeee eee eeeeeee ee 88 °M eee 8 eee eeeee eeeee. Meee eeee eee MeMM (88 μM, 8.88 eeee, 8.8 eeeee) eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eee eeeee Meeeeee eeee. Mee eeeeeeeee eeeeeee eee eeeeeeeeee ee 88 °M eeeee ee eeeeeeee eeeeeeee eee eeeeeeee ee MMM (8.8–88 e). Mee eeeeeeee eee eeeeeeee ee eeeeeee eee eeeeeee eeeeeee e eeeee eeee ee Meeeee eee eeeeee eee, eeeeeee eeee MM8Me8 (8 × 8 eM). Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeeee e eeeee eee, eeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 88:88) ee eeeeee eee eeeeeee eeeeeeee ee eeeeeeeee eeee.

References


Cookie-Einstellungen