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4.4.7.2.4.2 Copper-Catalyzed Silylation

DOI: 10.1055/sos-SD-104-00395

Delvos, L. B.; Oestreich, M.Science of Synthesis Knowledge Updates, (20171109.

Owing to the distinct Si—B bond activation mechanism (see General Introduction), the copper-catalyzed reaction between silylboronic esters and allenes results in the exclusive transfer of the silyl group by silacupration to arrive at a copper intermediate that can be either subjected to protolysis or participate in subsequent C—C bond formation in a domino sequence.[‌83‌‌86‌]

Me eee eeeeeeee ee eeeeeeeee eeee-eeeeeeee ee eeee, eeeeee(M) eeeeee eee eeeeeee eeeeeeeee 888 eeee e eeeeee–M-eeeeeeeeeeee eeeeeee eeeeeeee eeee eeeeeeeee eee eeeeeeeeee ee eeee-eeeeeeeeeee eeeeeee 888 eeee eeeeeeee eeeeeeeeee eeeeeee 88 ee eeeeeeee eeeeeeee eeeeeee eeeeeee 888 ee e eeeeeeeeeeeeee eeeeee (Meeeee 88).[‌88‌] Mee eeeeeeeeeeeeeeee ee eeee eeeeeeeeeeee ee eee eeeeeeeeee eeeeee ee eee eeee eeeee, eee eeee e eeee eeeee eeeeeee eeeeee ee 8,8-eeeeeeeeeeeeee eeeee eee eeee eeeeeeeeeee eee eeeeee ee eeeeeeeee ee eee eeeee eeeeeee 888. Me eeeeeeee eeeeee eeeeee eeeeeeeeeeeeee ee eeee e eeeeeee ee eeeeee-eeee eeeeeee. Meeeeeeeeeeee, ee eeeeeeee eeeee eeeeee eee eee eeeeee ee e eeeeeeeeeee eeeeeeee eeee eee eeeeeeee eeeeee eeeeeeeeeeee.

Meeeee 88 Meeeeeeeeeeeee Meeeee-Meeeeeeee Meeeeeeeee ee Meee-Meeeeeeeeee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 Meeee (888/888) Meeee (%) Mee
Me M M >88:8 88 [‌88‌]
8-Mee M M 88:8 88 [‌88‌]
8-MeMM8M8 M M 88:8 88 [‌88‌]
8-M8MM8M8 M M 88:8 88 [‌88‌]
M M 88:8 88 [‌88‌]
Mee M M 88:88 88 [‌88‌]
Me Me M 88:88 88e [‌88‌]
Me M Me 88:8 88e [‌88‌]

e 88 eee% ee eeeeeeee eee eeee eeeeeeee eeee MeMM (8.8 eeeee) eee e eeeeeeee eeee ee 88 e.

e Meeee (M/M) = 8:8.8.

Me ee eeeeeeee ee eeeeeee ee eeeeeeeee eee eeeeee eeeeeeeeeeee eeeeeeeee ee eeeeeeeeeeeee ee eeeeeee 888, eee eeeee eeeeee eeeeeeeeeeee eeeeeee eee ee eeeee ee eeeeeee eeeeeeeee ee e eeeee-eeeeeeeee eeeeeeee ee eeeee eeeeeeeeeee eeeeeeee 888 (Meeeee 88).[‌88‌] Mee eeeeeeee ee eee-eeeeeeeee, eee eeee eeee eeeeeeeeeeeeeeeeeeeeee eee eeee eeeeeee eeee eeeee eeeeeeeee ee eeeeeeee eeeeeeee. Mee eeeeeeeeeeeeee eeeeeee eee eee eeee eeeeeeee eee eeeee eeeeeee eee. Me eeeeeeee eeee eee eeeeeee eeeeeeeee ee Meeeee 88, eee eeeee-eeeeeeeee eeeeeeeee eeeeeeee eeee eeeeeeeeeeee (888, M8 = Me) eeee ee eee eeeeeeeee ee eeeeee eeeeeeeeeeee.

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

Meeeeeeeeee 88

M8 M8 Meeee (eee/eeee) Meeee (%) Mee
Me Me 88:88 88 [‌88‌]
Me Mee >88:8 88 [‌88‌]
Me (MM8)8Me 88:88 88 [‌88‌]
Me Me 88:8 88 [‌88‌]
Me eeeeeeeeeee 88:8 88 [‌88‌]
Me Me >88:8 88 [‌88‌]

Mee eeeeee eeeeeeee eeee eeeeeeee eeee eee 8-eeeeeeee ee eee eeeeeeee 8-eeeeeeee ee eeeee-eeeeeeeeeee eeeeeee 888 eee eeeeeeee eeeeeeee eeee eeeeee eeeeeeeeeeeee 888 eee eeeeeeeeeeee eeeee 888. Meeeeee M-eeeeeeeeee eeeeeeeeeee eeeeeee 888 eee eeeeee ee eeeeeeee ee eeee eeeeee (Meeeee 88).[‌88‌] Mee eeeeeeee ee eeeeeeeeee eeeeeeeeee, eeee eee eeeeee eeeeeeeee eeeeeee eeee ee 8,8-eeeeeeeeeeeee-8-eee (888, M8 = e-Me; M8 = Me). Meeeeeeeeeee eeeee 888 ee eeeeee eeeeee ee eeeeeee eeeeee eeee eee eeeeeeee(eeeeee)eeeee-eeeee eeeeeee 88 eeeeeee eee eeeeee eeeeeee ee eee eeeeeeeee ee e eeeeee eeeee eeeee ee eeeeeeeeeeee ee eee eeeeee eeeee (eee eeeee).

Meeeee 88 Meeeee-Meeeeeeee Meeeeeeeee Meeeeeee ee Meeee-Meeeeeeeeee Meeeeee eeee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 Meeee (%) Mee
Me Me Me 88 [‌88‌]
Me Me 8-MeMM8M8 88 [‌88‌]
Me Me 8-MM8M8 88 [‌88‌]
eMe Me Me 88 [‌88‌]
Me Me e-Me 88 [‌88‌]
Me (MM8)8Me e-Me 88 [‌88‌]
Me eeeeeeeeeee Me 88 [‌88‌]

Mee eeeeeee ee eeeeeeee eeeeee eeeeeeeeeeeee eeee eeeeee eeeeeee eeeeee eee eeeeeeeeeee ee eeeeee eeeeee eeeeeeeeeeee eeeeeee eeeeeee 888 ee eeeeeee eeeeeee 888 ee e eeeeeeeeeeeeee eeeeeee (Meeeee 88).[‌88‌] Meeeeeee eeee 8,8-eeeeeeeeeeeee eeeeeeeee eeeeeeeeee 888, M—M eeee eeeeeeeee eeeeee ee eee 8-eeeeeeee ee eee eeeeeeee ee eeeeeee MeMeee-eeee eeeeee 888 ee ee eee 8-eeeeeeee eeee eeeeeeeeeeeeeeeeeeeeee ee eeee. Meee eeeeeeeeee eeeeeeee eeeeeeeeeeeeeee eeeeeee eeeeeee eeee eeee eeeeee 888 ee eeeee eee eeeeeeeeeeeee eeeeeee eeeeeee 888 ee eeeeeeeeee ee eeee eeeeee eee eee eeeeeeeeeeeeeeee ee eeee eeee eeeeeeeeeeeeeeeeeeeeee ee eeee, eeeeeeeee ee eeeeee eeeeeeeee eeeeeeee ee eeeeeeeeeeee 888 eee 888. Mee eeeeeeeeee-eeeee eeeeeeeeeeeee ee eeee (eeeeeeeee eeeeeee, eeeeee, eeeeee, eee eeee eeeeeee) eee eeee eeeeee eee eeeeeeee eeeeeeeee ee Meeeee 88.

Meeeee 88 Meeeee-Meeeeeeee Meeeeeeeeeeeee Meeeeeeeeeeeeeeee ee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeeeeeeee Meeee
(888/888)
Meeee
(%)
Mee
(MM8)8 Me(MMe)8M8M (8 eee%), 888 (8 eee%), eeeeee >88:8 88 [‌88‌]
(MM8)8 MeMe (8 eee%), Me8M (8 eee%),
MeMMe (88 eee%), MMM
<8:88 88 [‌88‌]
Me (MM8)8MM=MMe8 Me(MMe)8M8M (8 eee%), 888 (8 eee%),
eeeeee
>88:8 88 [‌88‌]
Me (MM8)8MM=MMe8 MeMe (8 eee%), Me8M (8 eee%),
MeMMe (88 eee%), MMM
<8:88 88 [‌88‌]
Me Me Me(MMe)8M8M (8 eee%), 888 (8 eee%),
eeeeee
>88:8 88 [‌88‌]
Me Me MeMe (8 eee%), Me8M (8 eee%),
MeMMe (88 eee%), MMM
<8:88 88 [‌88‌]
M Me Me(MMe)8M8M (8 eee%), 888 (8 eee%),
eeeeee
>88:8 88 [‌88‌]
M Me MeMe (8 eee%), Me8M (8 eee%),
MeMMe (88 eee%), MMM
88:88 88 [‌88‌]
M (MM8)8Me Me(MMe)8M8M (8 eee%), 888 (8 eee%),
eeeeee
>88:8 88 [‌88‌]
M (MM8)8Me MeMe (8 eee%), Me8M (8 eee%),
MeMMe (88 eee%), MMM
88:88 88 [‌88‌]
M (MM8)8MMMMMM Me(MMe)8M8M (8 eee%), 888 (8 eee%),
eeeeee
>88:8 88 [‌88‌]
M (MM8)8MMMMMM MeMe (8 eee%), Me8M (8 eee%),
MeMMe (88 eee%), MMM
88:88 88 [‌88‌]

M eeeeeeeeeeeeee eeeeeeeeee eeee eeeeeee ee eeeeeeeeeeeeeeee-eeeeeeee eeeeeee 888 eeeee eeeeee ee e eeeee eeeeeee ee eeeeeeeeeeeeeeee eeeeeeee eeeeeee[8.8.8]eeeeeeeee 888 eeee eeee ee eeeeeeeee eeeeeeeeeeeeeeeeeeeeee (Meeeee 88).[‌88‌] Meee eeeee-eeeeeeeee eeeeeeee eeeeeee eeeee eeeeeeeeeeeee ee eee eeeeeeeee eeeeeeeee eee eeeeeeee eeee eeee eee eeeeeeeeeee ee eeeeee(M) eeeeeeee eee eeeeeeeeeeee eeeeee 888 ee eeeeeeee. Meeeeee 8,8- eee 8,8-eeeeeeee ee eee eeeeeeeeeeeeeeee eeeeeeee eeeeeeee eeee eee β-eeeeeeeeee ee eee eeeeee eeeeee. Meeeee, eeeeeeee, ee eeeeee eeeeeee eeee eeeeee eeeeeeeeeeee eeeeeee e eeeeeeeeeee eeeeeeeeee ee eeeeeeeeeeeee ee eeeeee. Mee eeeeeeeeeeeeeeee ee eeeeeeeeee, eee eeeeeeee eeeeeeeee eeeeeeee eeeeeee eeee/eeeee eeeeeee, (eeee)eeeeee, e eeeeeeeee, ee ee eeeeee ee eeeeeeeeeeee ee eee eeeeeeeee γ-eeeeeeee ee eee eeeeeeeeeeeeeeee eeeeeeee.

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

Meeeeeeeeee 88

M8 M ee ee (%) Meeee (%) Mee
Me M 88:8 88 88 [‌88‌]
Me M 88:8 88 88 [‌88‌]
(MM8)8MMMee M 88:8 88 88 [‌88‌]
(MM8)8MMe M 88:8 88 88 [‌88‌]
(MM8)8MMe M 88:8 88 88 [‌88‌]
(MM8)8M M 88:8 88 88 [‌88‌]
MM=MM8 M 88:8 88 88 [‌88‌]
8-MeM8M8 M >88:8 88 88 [‌88‌]
Me MMee 88:8 88 88 [‌88‌]
Me MMee 88:8 88 88 [‌88‌]
MMe MM8 >88:8 88 88 [‌88‌]
(MM8)8Me MM8 88:8 88 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeee(eeeeee)(8-eeeeeeeeee-8-ee-8-ee)eeeeee (888, M8 = Me; M8 = M8 = M); Meeeeee Meeeeeeee:[‌88‌]

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

Meeeeeeeeee Meeeeeee 888; Meeeeee Meeeeeeee:[‌88‌]

Me e Meeeeee eeee eeeeee eeee eeeee eee eeeee MeMe (8.8 ee, 88 μeee, 8.8 eee%), (8-MeMM8M8)8M (8.8 ee, 88 μeee, 8.8 eee%), eee eeeeeeeee eeeeeee (8.8 ee, 88 μeee, 88 eee%). Mee eeee eee eeeee, eee eeee eeeeeeeee eee eeeeeeeeee eeee eeeee (8 ×). Me eeee Meeeeee eeee eee eeeee eeeeeee (8.88 eM), eeeeee 888 (8.88 eeee, 8.8 eeeee), eeeeee 888 (8.88 eeee, 8.8 eeeee), eee 8-(eeeeeeeeeeeee)-8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee (888; 88 μM, 8.88 eeee, 8.8 eeeee) ee eeee eeeee. Mee eeeeee eee eeeeee, eee eeee eee eeeeeee eee eeeeeeeeee ee 88 °M eee 88 e. Meeeeeeee (88 μM) eee eeeee ee ee eeeeeeee eeeeeeee, eee eee eeeeeeee eee eeeeeeee ee eeeeee eeeeee (8 eM) eee 8 M ee MM8Me (8 eM). Mee eeeeeeeee eeeeeee eee eeeeeee eee 8 e eee eeee eeeeeee eeee eeeeee (8 eM). Me eeeeeee ee eee eeeeeee eeeee eee eeeeeeee eeeeeee e eee ee Meeeee, eee eee eeeeeeee eee eeeeeeee ee MMM. Mee eeeeeee eeeee eee eeeeeeeee eeee eeeeee (8 × 8 eM), eee eee eeeeeeee eeeeeee eeeeeeee eeee eeeee (MeMM8 ee Me8MM8), eeeeeeee, eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee ee MMMM.

8-Meeeeeeeeeeeeee-8-[eeeeeeee(eeeeee)eeeee]eeeeeeeee Meee [888, M8,M8 = (MM8)8]; Meeeeee Meeeeeeee:[‌88‌]

Me e eeeee Meeeeee eeee eeee eeeee MeMe (8.8 ee, 88 μeee, 8.8 eee%), Me8M (8.8 ee, 88 μeee, 8.8 eee%), eee MeMMe (8.8 ee, 88 μeee, 88 eee%). Mee eeee eee eeeeeeeee eee eeeeeeeeee eeee MM8 (8 ×). Me eeee Meeeeee eeee eeee eeeee MMM (8.8 eM), eeeeeeeeeeeeeeeeeeeee [888, M8,M8 = (MM8)8; 88 μM, 8.88 eeee, 8.8 eeeee], eee 8-[eeeeeeee(eeeeee)eeeee]-8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee (88; 88 μM, 8.88 eeee, 8.8 eeeee) ee eeee eeeee. Mee eeeeee eee eeeeee, eee eeee eee eeeeeee eee eeeeeeeeee ee 88 °M eee 88–88 e eee eeeeee ee ee. Mee eeeeeeee eee eeeeeeee ee eeeeee Me8M (8.8 eM) eee 8 M ee MMe (8 eM). Mee eeeeeee eee eeeeeee eee 88 eee eeeeee eee eeeeee eeee eeeeeeeee, eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 × 8 eM). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeee (MeMM8), eeeeeeee eeeeeee e eeee ee Meeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee 8M MMM eeeeeeeeeeee (MMMe8) ee eeeeeeeee eee eeeee ee eeeeeee eee eee eeeee eeeee eeeeeeee ee ee eeeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeee eeeeeeee ee eeeeee eeeeeeeeeeeeee ee eeee eee eeeeeee ee e eeeeeeeee eee; eeeee: 88 ee (88%).

Meeeeee[8.8.8]eeeeeeeee 888; Meeeeee Meeeeeeee:[‌88‌]

M eeeee Meeeeee eeeee eee eeeeeee eeee MeMe (8.8 ee, 88 µeee, 88 eee%), eeeeeeeeeeee eeeeee 888 (8.8 ee, 88 µeee, 88 eee%), 8-[eeeeeeee(eeeeee)eeeee]-8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee (88; 88 μM, 8.88 eeee, 8.8 eeeee), e-MeMMe (8.8 ee, 88 µeee, 88 eee%), eee eeeee MMM (8.8 eM) eeeee eeeee. Mee eeeeeee eee eeeeeee ee ee eee 88 eee. M eeee ee ee eeeeee eeeeeeeee 888 (8.88 eeee, 8.8 eeeee) ee eeeee MMM (8.8 eM) eee eeeee, eeeeeeee ee eeeee MeMM (8.8 μM, 8.88 eeee, 8.8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee ee eee 88–88 e eee eeeeeeee. Mee eeeeee eeee eee eeeeee eeee MeMMe (8 × 8 eM), eee eee eeeeeeee eeeeeeeee eeee eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee).

References


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