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4.4.7.2.6.3 Copper-Catalyzed 1,4-Silylation of Ynones and Derivatives Thereof

DOI: 10.1055/sos-SD-104-00395

Delvos, L. B.; Oestreich, M.Science of Synthesis Knowledge Updates, (20171137.

Copper-catalyzed 1,4-silylation with silylboron reagents as the source of the silicon nucleophile is not limited to carbonyl-/carboxy-conjugated double bonds. Ynones and other triple bonds in conjugation with electron-withdrawing groups also react regioselectively to provide access to functionalized vinylic silanes.[‌111‌‌113‌]

Mee eeeeeeeeee ee eeeeeeeeeeeeee eeeeee eeeeeeee eeeeeee ee eeeeeeee eeeee eee eeeeee eeeeeeeeeee ee eeeeee(MM) eeeeeee eee 8-eeeeeeeeeeeeee ee eeeeeeeee ee eeeeeee eeeee eeeee eeeeeee eeeeeeeeee.[‌888‌] β-Meeeeeeeeee eeeeeeeeee eeeeeeeee eee eeeeeee 888 eeeee eeeeeeeeeeeee ee eeee M-eeeeeeeeee eeeeeee eeeeeee 888 eeee eeeeeeee ee eeeeeeeee eeeeeeeeeeeeeeeeeee eee ee eeee eeeeee (Meeeee 88). Me ee eeeeeeeeee eeee eee ee eee eeee eeeeeeee eeeeeeeee eeeeee, eeee eeee eeee e eeeeee eeeee ee eee β-eeeeeeee eeeee eeeeeeeee 8,8-eeeeeeeeee (8,8/8,8 eeeee = 8:8); eee eeeee eeeeeeeeeee ee eeee eeeeeeee eeeeeee ee eeeeeeee ee eee β-eeeeeeee eeeeeeeeeee. Meeeeeeeee eeeeeee eeeeeee eee eeeeeeeeeeeee eeeeeee eeee eeeeeeeeeeeee eeeee M eeeeeeeeeeeee. Meee eee eeee eeeeeeeee eeeee, ee eeeeeeeee 8,8-eeeeeeeeee ee eeeeeeee, eeee ee eee eeee ee e eeeeee eeeeeeeeeee ee M8 eeeee.

Meeeee 88 Meeeee-Meeeeeeee Meeeeeeeeeeeeeeeee 8,8-Meeeeeeeee ee Meeeeeeeee Meeeeeeee eee Meeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 Meeee (M/M) Meeee (%) Mee
Me M 88:88 88 [‌888‌]
(MM8)88Me M 88:8 88 [‌888‌]
Me M 88:88 88 [‌888‌]
Me M 88:88 88 [‌888‌]
MM8MMeMe M 88:8 88 [‌888‌]
M 88:88 88 [‌888‌]
eeeeeeeeeee M 88:8 88 [‌888‌]
Me Me 88:88 88 [‌888‌]
Me Me 88:88 88 [‌888‌]

Me eee eeeeeeee-eeeeeeeeeee eeeee ee eeeeeeee ee ee eeeee ee eeeee eeeee eeeeeeeee eeeeeeeee eeeeeeeeee, eee eeeeeeeeee eeeeeeee eeee eeeeeeeee M eeeeeeeeeee ee eeeeeeee eeeeeee eeeeeee 888 ee eeeeeeeee eeeeee. M eeeeeeeee ee eeeeeeee ee eeeeeeeee ee Meeeee 88.[‌888‌] Meeeeeeeee eeeeee 888 eeee eeeeeeeeeeeeeeee ee eeeeeeeeeeeeee eeeee eeeeeeeeeeee eeeee eeeeeee ee eee eeeeeee eeeeeee 888; e eeeeeeee eeeeee eee ee eeeee-eeeeeeeeeee eeeeeeeee eee eee eeeeeeeeee. Meeeeeee, eeeeeee ee eeee ee eeeeeeeeeeeeee eeeeeeee eeee eeeeeeeeeeee eeee ee eeeeeeeee eeeeeee. Meeeeeeee ee eee eeeee eeeee, e.e. eee ee eeeeee eeeeeeeee ee eeee-eeeee eeeeeeeee, eee ee eeeeeeeee ee eee eeeeeeeeee. Meeeeeee 888 (M8 = MMe8) eeee eeeeeeee-eeeeeee eeeee ee eeee eeeeeeeeeeee eee eeeeeeeeeee ee eee eeeeeeeeeeeee eeeeeee eeeeeee 888 (M8 = MMe8) eeeeeee eeeeeeeeeee eeee eeeeeeeee eeeeeeeeeeeeeeeee.

Meeeee 88 Meeeee-Meeeeeeee Meeeeeeeeeeeeee 8,8-Meeeeeeeee ee Meeeeeeeee Meeeee eee Meeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 Meeee (%) Mee
Me MMe 88 [‌888‌]
M MMe 88 [‌888‌]
Me MMe 88 [‌888‌]
MM8MMMMMM MMe 88 [‌888‌]
MM8MMe8 MMe 88 [‌888‌]
8-MeMM8M8 MMe 88 [‌888‌]
8-M8MM8M8 MMe 88 [‌888‌]
Me MMe 88 [‌888‌]
(MM8)8Me Me-Me 88 [‌888‌]
Me MMe8 88 [‌888‌]
Me MMe8 88 [‌888‌]

Mee eeeee ee eeee eeeeeeee eee eeeeeeeeeeeee eeeeeeee ee eee eeeeeeeeeeee ee eeeeeeeeee 888 (Meeeee 88).[‌888‌] Me eeee eeee, eeeeee(M) eeeeeee/eeeeeeeeeeeeeeeeee eeeeeee eeee e eeeeeeeee ee eee eeeeeee eeeeeeee eee eee 8,8-eeeeeeeeee ee ee eeeeeeeeee eeeee ee eeeeeeeeee eeeeeeeee, eeeee ee eeeeeee eeeee eee ee eeee eeeeeeeeeee. Me eeeeeeee ee eeeeeee eeeeeee eeeeeeee ee eeeeeeeeee eeeeee eee eeeeee (eee eeeee), e eeeeeee ee eeeeeeeeeeeee eeeeeeeeee 888 eeee ee e eeeeeeeeee eeee, e eeeeeee, ee e eeeeeee eeeee eeeeeeeeeeee. Me eeee ee eeeee eeeeeeee eeeee, eee eeeeeee eeeeeee eeeeee 888 ee eeeeee eeeeee eeeeeeeeeee eeee e eeeeeeeeeeeeeeeee ee >88:8 ee eeeee ee eee M-eeeeee. Mee eeeeeeee eeeee eee ee eeeeee eee ee ee eee eeeeeeeeeee eeeeeeeee eeeeeee eeeeee ee eeeee ee eeeeeeeeeee.

Meeeee 88 Meeeee-Meeeeeeee Meeeeeeeeeeeeee 8,8-Meeeeeeeee ee Meeeeeeeeeeeee-Meeeee Meeeeeeeee ee Meeeeeee Meeeeeeee[‌888‌]

Meeeeeeeeee 88

MMM Meeee (M/M) Meeee (%) Mee
MM8M >88:8 88 [‌888‌]
Me >88:8 >88 [‌888‌]
MM >88:8 >88 [‌888‌]

Mee eeeeeeeee eeeeeeeeeeeee eee eeeee ee e eeeeeee eeeeeeeeeeee ee eeeeee-eeeeeeeee eeeeeeeeee ee eeeeeee, ee eeeee eeeeeee eeeeeeeeee eeeeee eeee eeeeeeeee ee eee β-eeeeeeee eeee eeeeeeeeeeee eeeee 88 ee eeeeeee eeeeeeeeee eeee eeeeee.[‌888‌] Mee eeeeee eeeeeeee eee, eeeeeee, eeeeee eeee 88 eee% ee eeeeee(M) eeeeeee eeeee eeeeeeee. Meeeeeeeeeee, eeee eeeeee eeeeeeee eeee eeeeee eeeeeeee.

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

Meeeee 88 Meeeeeeeeeeeeee Meeeee/Meeeeeeee-Meeeeeeee Meeeeeeee ee Meeeeeeeeeeeeeee Meeeeee[‌888‌]

Meeeeeeeeee 88

M8 Meeeeeeeee Meeee
(M/M)
Meeee
(%)
Mee
(MM8)8Me MeMe (8 eee%), Me8M (88.8 eee%), Me(MMe)8 (8 eee%),
e-MeMM (88 eee%), MM8Me8, 88 °M, 88 e
88:8 88 [‌888‌]
(MM8)8Me 888 (8 eee%), Me(MMe)8 (8 eee%), e-MeMM (88 eee%),
MM8Me8, 88 °M, 88 e
8:88 88 [‌888‌]
(MM8)8MMM8Me MeMe (8 eee%), Me8M (88.8 eee%), Me(MMe)8 (8 eee%),
e-MeMM (88 eee%), MM8Me8, 88 °M, 88 e
88:8 88 [‌888‌]
(MM8)8MMM8Me 888 (8 eee%), Me(MMe)8 (8 eee%), e-MeMM (88 eee%),
MM8Me8, 88 °M, 88 e
8:88 88 [‌888‌]
Me MeMe (8 eee%), Me8M (88.8 eee%), Me(MMe)8 (8 eee%),
e-MeMM (88 eee%), MM8Me8, 88 °M, 88 e
88:8 88 [‌888‌]
Me MeMe (8 eee%), Me8M (88.8 eee%), Me(MMe)8 (8 eee%),
e-MeMM (88 eee%), MM8Me8, 88 °M, 88 e
88:8 88 [‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeee (M)-8-[Meeeeeee(eeeeee)eeeee]eee-8-eeeeee (888, M8 = Me; M8 = MMe); Meeeeee Meeeeeeee:[‌888‌]

Meeee eee-8-eeeeee (888, M8 = Me; M8 = MMe; 88 μM, 8.88 eeee, 8.8 eeeee), 8-eeeeeeeeeeeeee (8.8 μM, 88 µeee, 8.8 eee%), 8-[eeeeeeee(eeeeee)eeeee]-8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee (88; 888 μM, 8.888 eeee, 8.8 eeeee), eee e 8.8 eM eeeee eeee ee MeMM8 ee M8M (8.8 eM, 8.8 μeee, 8.8 eee%) eeee eeeee eee eeeeeee. Meeee 8 e, eeeeee (8 eM) eee eeeee ee eeeeee eee eeeeeeee. Mee eeeeeee eeeee eee eeeeeeeee eeee eeeeee (8 ×). Mee eeeeeeee eeeeee eeeeee eeee eeeeee eeee M8M (8 ×) eee eeeee (MeMM8). Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 8:8) eee eeeeeeee ee e eeeeee eee; eeeee: 888 ee (88%).

Meeeeee Meeeeee 888; Meeeeee Meeeeeeee:[‌888‌]

Me ee eeeee-eeeeee eeeeeeeee eeee, eeeeee eeee e eeeeee eeeeee eeeee e eeeeeeee eeeee eeee, eeee e eeeeeeeeee eeee eeee, eee eeeee MeMMe (8.88 ee, 8.8 μeee, 8.8 eee%) eee Me8M (8.88 ee, 8.8 μeee, 8.8 eee%). Mee eeeee eee eeeeeeee ee ee eeeee eeee eee eeeeee ee eee eeee eeeeeeeeee eeeee eee 8 eee ee eeeeeeeee e eeee eeeeee eeeeeee eee eeeeee. Meeee 8 eee, eee eeee eeeeee eee eeeeeee. M eeeeeeee 8 ee% eeee ee eeeeeeeeee 888 ee M8M (8.888 eM) eee eeee eeeee ee eee eeee eee eee eeeeeee eee eeeeeee ee eeeeeeeeee ee eeeeeeee eeeeeee eeeeeeeee eee 8 eee. M eeeeeee/eeeeee eeeee eee eeeeeee eeeeeeee eeee eee eeeeeeee ee eee eeeeeeeeee eeee ee eee eeeeee eeeeeeee. Me eeeeee 888 (8.88 eeee, 8.8 eeeee) eee eeee eeeee eee eeeeeee eee eee eeeeeee eee eeeeeeeeee eeeeeee eee 8 eee. 8-[Me­eeee­ee(eeeeee)eeeee]-8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee (88; 88.8 ee, 8.888 eeee, 8.88 eeeee) eee eeee eeeee eee eeeeeee, eee eee eeeeeeee eee eeeeeeeeee ee ee eee 8 ee 88 eee. Me eeee eeeee, eee eeeeeeee eee eeeeeeee ee eeee eeee, eee eee eeeeeeeee eeee eeeeeeeee eeeeeeeee ee MMM ee eeeeeeeee eee eeeee ee eeeee eeee eeeeeeeeee eee eeee eeeeeee. Mee eeeeeeee eee eeeeeeee ee eeeeeee eee eeeeeee eeee e eeeee eee ee eeeeee eee. Mee eeee eee eeeeee eeee e eeeeeee eeeeee ee eeeeeee (eeeeeee Me8M ee MeMMe), eee eee eee eee eeeeeee eeee eeeeeeeeee eeeeeee ee eeeee eee eeeeee. Meeeee eeeeeeeeeee eeeeeeee eee eeeee eeeeeeeee, eeeee eeee eeee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/Me8M).

Meeeeeeeeeeeeeee Meeeeee (M)-888; Meeeeee Meeeeeeee:[‌888‌]

M eeeee-eeeee Meeeeee eeeee eee eeeeeeeeeeee eeeeeee eeee Me(MMe)8 (8.8 ee, 8.8 μeee, 8.8 eee%), Me8M (8.8 ee, 88 µeee, 8.8 eee%), eee MM8Me8 (8.8 eM). Mee eeeeeee eee eeeeeee ee ee. Meeee 8 eee, eeeee eeeeee eeeeeeeee (8.88 eM, 8.8 eeee, 8.8 eeeee) eee eeeee, eee eee eeeeeeeee eeeeeee eee eeeeeee eee ee eeeeeeeeee 8 eee. Meeeeeeeeeeeee, eeeeeee eeeee-eeeee Meeeeee eeeee eee eeeeeee eeee MeMe (8.8 ee, 88 µeee, 8.8 eee%), Me8M (88 ee, 8.88 eeee, 88 eee%), eee e-MeMM (8.8 ee, 88 µeee, 88 eee%) ee MM8Me8 (8.8 eM) eee eeee eeeeeee eee eeeeeee eee 8 eee. Meee eee Me(MMe)8 eee eeeeeeeeee eeeeeeeee, eee eeeeeeeee eeee eee eeeeeeeeeee eeee eee Meeeeee eeeee eeeeeeeeee eee eeeeee eeeeeeee, eeeeeeeeeee eeeeeeee ee ee eeeeee 888 (8.88 eeee, 8.8 eeeee) ee MM8Me8 (8.8 eM). Mee eeeeeee eee eeee eeeeeeee eeeeee ee 88 °M, eee 8-[eeeeeeee(eeeeee)eeeee]-8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee (88; 8.88 eM, 8.88 eeee, 8.8 eeeee) eee eeeeeee eeeee ee eeeeeee. Meeee 88 e, eeeeeeeee eeeee/Me8M (8:8; 8.8 eM) eee eeeee ee eee eeeeeee. Mee eeee eee eeee eeeeeeee eeeeeee e eeee ee eeeeee eee eeeeeee eeee eeeeeeeee eeeee/Me8M (8:8). Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeee e eeeeeeeee eeeeeee. Meeeeeeeeeeeeeeee eee eeeeeeee eee eeeeeeee eeeeeeeeeee, eee 8,8-eeeeeeeeeeeeee eee eeee ee ee eeeeeeee eeeeeeee. Meeeee eee eeeeeeeeeeeeee eeeeee eeee eeeeeeeeee ee MMM eeeeeeeeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee MMMM ee eeeee eeeeeeeeeeeeee.

References


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