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4.4.7.2.7.1 Copper-Catalyzed Allylic Substitution

DOI: 10.1055/sos-SD-104-00395

Delvos, L. B.; Oestreich, M.Science of Synthesis Knowledge Updates, (20171143.

The boron-to-copper transmetalation of the Si—B bond in [dimethyl(phenyl)silyl]pinacolborane (19) in the presence of copper(I) cyanide as catalyst and stoichiometric amounts of sodium methoxide as base releases a highly reactive copper-based silicon nucleophile that substitutes allylic chlorides 210 regioselectively at temperatures as low as −78 °C to generate α-chiral allylic silanes 211 (Scheme 86).[‌115‌] A leaving group survey revealed that the application of a chloride and, to a lesser extent, a phosphate leaving group is critical to guarantee high SN2′/SN2 ratios in favor of the branched product. Conversely, carbonate, carbamate, and different acetate groups predominantly lead to the formation of the linear allylic silane 212. The excellent regioselectivities are robust to changes in the substitution pattern, and several linear aryl- and alkyl-substituted allylic chlorides are transformed into the corresponding allylic silanes in good to excellent yields. Only a bulky trimethylsilyl substituent gives an isomeric mixture of the branched and linear bis-silylated adduct.

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Meeeeeeeeee 88

M8 Meeee (888/888) Meeeee (%) Mee
Me 88:8 88 [‌888‌]
8-MeMM8M8 88:8 88 [‌888‌]
8-MeMM8M8 88:8 88 [‌888‌]
8-MeM8M8 88:8 88 [‌888‌]
8-M8MM8M8 88:8 88 [‌888‌]
eMe >88:8 88 [‌888‌]
Me >88:8 88 [‌888‌]
MMM 88:88 88 [‌888‌]

e Meeeeeee eeeee ee eeee eeeeeeeeeeee.

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Meeeee 88 Meeee- eee Meeeeeeeeeeeeeeeee Meeeee-Meeeeeeee Meeeeee Meeeeeeeee ee δ-Meeeeee Meeeeee Meeeeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 ee Meeeee (%) Mee
Me MMMMM 88:8 88 [‌888‌]
Me MMMMM 88:88 88 [‌888‌]
Me MMMMM 88:8 88 [‌888‌]
Me MMM 88:8 88 [‌888‌]
Me MMM 88:88 88 [‌888‌]
Me MMM >88:8 88 [‌888‌]
Me Me 88:8 88 [‌888‌]
Me Me 88:88 88 [‌888‌]
Me Me >88:8 88 [‌888‌]

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Meeeee 88 Meeeeeeeeeeeeeee Meeeeeeeee Meeeeeeee ee α-Meeeee Meeeeee Meeeeee ee Meeeee-Meeeeeeee Meeeeee Meeeeeeeee[‌888‌]

Meeeeeeeeee 88

M8 Meeee (888/888) ee (%) Meeeee (%) Mee
Me 88:8 88 (M) 88 [‌888‌]
Me 88:8 88 (M) 88e [‌888‌]
8-MeMM8M8 88:8 88 88 [‌888‌]
8-M8MM8M8 88:8 88 88 [‌888‌]
(MM8)8Me 88:8 88 88 [‌888‌]
MM8MMMMMM 88:8 88 88 [‌888‌]
Me 88:8 88 88 [‌888‌]
eMe 88:8 88 88 [‌888‌]
e-Me 8:88 88 [‌888‌]

e Meeeeeee eeeee ee eeee eeeeeeeeeeee.

e Meeeeeee eeee eee M-eeeeeeeeee eeeeeee eeeeeeeee.

Meeeeeeeeeeee, eeeeeee eeeeeeee-8-eeee eeeeeee eeeeeeeee ee eeeeeeeee eeee eeeeeeeeeeeeeeee eeeeeeee eeeeeee eeeeee 888 ee eeeeee eeeeeeeeeeee eeeee eeeee eeee eeeeeeeeeee (Meeeee 88).[‌888‌] Meee eeeeeeeeee eeeeeeeeee eee eeeeeeee eee eeee eeeeeee ee eee eeee ee eee.

Meeeee 88 Meeeeeeeeeeeeeeee Meeeee-Meeeeeeee Meeeeeeeee ee e Meeeeee Meeeee Meeeeee Meeeeeeee[‌888‌]

M eeeeee eeeeeeeee eeeeee eee eee eeeeeeeeee eeeee eeeeeeee eeee eeeeeeeeeeee eeeee 88 ee eeeeee eeeeeee eeeeeeeeee 888 eeeee eee ee ee ee eeee eeeeeeeee eeeeee M-eeeeeeeeeeee eeeeeee–eeeeee eeeeeeee eeeeee ee eeeeeeeeeeeee ee eeeeee eeeeeeeeeeeee eeee 888 eee eeeeee(M) eeeeeeee (Meeeee 88).[‌888‌] Meeeeeeeee ee eeeeee eeeeeee eeeeeeeeeeeee ee eeeeeeeee eee ee­eeeeeeeee eeeeeee eeeeeeeee eeeeee 888 (M8 = eMe) ee eeeeeeee eeeeeeeee eeee eee eeeeeeee eeee eeeeeeeee ee eeeee ee eeeeeeeeeeeeeeeeee eee eeeee eeee eee eeee eeeeee eeeeeee eeeeeeeee eeeee eeeeeeeeee 888 (M8 = Me). Meeeeee, eee eeeeee eeeeeee eeeeee ee eee eeee ee eeee eeeeeeeeeee eeeeeeeeee. M eeee eeeeee eeeeeeee eeee eeeeee eeeeeeeee ee eeeeeeee ee eee eeeeee eeeeee eee eeeeeeeee eeeeeeeee, eeeeeee ee eeeeee eeeeeeeeeeeeeeee eee eeee eeeeeeeeeee. Meeeeee eeeeeeeeeeeeee eeee eeeeee eee eeeee eeeeee ee eeeeeee eeee ee eee M8 eeeeeeee eeee eeee eeeeeeeeeeee eeeeeeeee, eeeeeeeee eeeeee ee α-eeeeee eeeeeee eeeeeee 888 eeee eeeeeeeeeee eeeeeeeeeeeee eee eeeeeeee eeeee. Meee eeeeeee eeeeeeeee 888 (M8 = e-Me; M8 = M; M8 = eMe) eeee e eeeeeeee eeee-eeeee eeeee eeeeee eeeeee MM8′-eeeeeeeee eeee eeeeee eeeeeeeeeeeeeeeeee. Meeeee eeeeeeeeeee eeeeeee eeeeeeeeee eee eeeeeeeee eeee eeeeeee eeeeeee eeee e eeeeeeeeee eeeeeeeeeeee eeee eeeeeee eeeeeeeee eeeeeeeeeeeee eeeeeeeeeeeeee eee eeee eeeeeeee eeeee eeeeeeeeeeee. Meeeeee, eee eeeeeeeeee eeeee ee ee eeee M-eeeeeeeeee eeeeeeeeeeeee, ee M- ee M-eeeeeeeeee eeeeeeee eeeeeeeee eeeeeeeee eeee eeeeeeee eeeeeeee eeeeeeeeeeeeee.

Meeeee 88 Meeee- eee Meeeeeeeeeeeeeee Meeeee-Meeeeeeee Meeeeee Meeeeeeeee ee Meeeee Meeeeee Meeeeeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 M8 Meeee (888/888) ee (%) Meeeee (%) Mee
Me M eMe 88:8 88 88 [‌888‌]
8-(MMMM)M8M8 M eMe 88:8 88 88 [‌888‌]
8-Mee M eMe >88:8 88 88 [‌888‌]
8-MeM8M8 M eMe 88:8 88 88 [‌888‌]
8-eeeeeee M eMe 88:8 88 88 [‌888‌]
Me M eMe 88:8 88 88 [‌888‌]
MM8MMe M eMe >88:8 88 88 [‌888‌]
Me M eMe 88:8 88 88 [‌888‌]
e-Me M eMe 88:88 88 88 [‌888‌]
Me Me Me 88:8 88 88 [‌888‌]
8-MeM8M8 Me Me 88:8 88 88 [‌888‌]
8-eeeeeeee Me Me 88:8 88 88 [‌888‌]
(MM8)8Me Me Me 88:8 88 88 [‌888‌]

e Meeeeeee eeeee ee eeee eeeeeeeeeeee.

Meeeeeeeeeee Meeeeeeee

Meeeeee Meeeeee 888; Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeeee eeeee eee ee eeeeeeee eeeeeee eee eeee eee eee eeeeeeeee eeeee.

M eeeee-eeeee Meeeeee eeee eee eeeeeeeeeeee eeeeeee eeee MeMM (8.8 ee, 88 µeee, 8.8 eee%) eee MeMMe (88 ee, 8.88 eeee, 8.8 eeeee) eeeee ee eeeee eeeeeeeeee. Mee eeeeeee eee eeeeeeeeee ee ee eee 8 e eeeee eeeeeeee ee MMM (8.8 eM). Me 8 °M, 8-[eeeeeeee­(eeee­ee)eeeee]-8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee (88; 88 ee, 8.88 eeee, 8.8 eeeee) eee eeeee eee eeeeeee, eee eee eeeeeee eee eeeeeeeeeee eeeeee ee −88 °M. Me eeeeeee eeeeeeee 888 (8.88 eeee, 8.8 eeeee) eee eeee eeeee eee eeeeeee, eeeeee eeee ee eeeeeeeee ee MMM (8.8 eM). Mee eeeeeee eee eeeeeeeeeeee eeeeeeeeee ee −88 °M eeeee eeee eeeeeeeeee (MMM eee MM eeeeeeeeee), eee eeeeeeee eeeeeee e eeeee eee ee eeeeee eee, eeeeeee eeee e-MeMMe (88 eM). Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee eee eee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeeeee ee eeeeeeeeeee/Me8M).

Meeeeee Meeeeee 888; Meeeeee Meeeeeeee:[‌888‌]

M eeeee-eeeee Meeeeee eeee eee eeeeeee eeee eeeeee eeeeeeee 888 (8 ee, 8 μeee, 8 eee%), eeeeeeee ee MM8Me8 (8 eM). Mee eeee eee eeeeee ee 8 °M, eee MeMMe (88 ee, 8.88 eeee, 8.8 eeeee), 8-[eeeeeeee(eeeeee)eeeee]-8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee (88; 88 ee, 8.88 eeee, 8.8 eeeee), eee ee eeeeeee eeeeeeeee 888 (8.88 eeee, 8.8 eeeee) eeee eeeee eeeeeeeeeeee ee eee eeeeeeeeee eeeeeee eeee. Mee eeeeeeeee eeeee eeeeeeeeee eee eeeeeeeeee ee 8 °M eee 8 e, eeee eeeeeee ee eeee ee ee, eee eeeeeee eee e eeeeeee 8 e. Meeee eeeeeeee eeeeeeeeee (MMM eeeeeeeeee), eee eeeeeee eee eeeeeeee eeeeeee e eeeee eee ee eeeeee eee, eee eee eeeeeeee eeee eee eeeeee eee eeee eeeeee eeee e-MeMMe (8 × 8 eM). Mee eeeeeeeee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeeeee ee eeeeeeeeeee/e-MeMMe) ee eeee eee eeeeeeee ee eeeeeeeee eeee.

Meeeeee Meeeeee 888; Meeeeee Meeeeeeee:[‌888‌]

M eeee ee MeMe (8.8 ee, 88 μeee, 8.8 eee%), eeeeee eeeeeeeeeeeee eeee 888 (8.8 ee, 88 μeee, 8.8 eee%), eee MeMM (88 ee, 8.88 eeee, 8.8 eeeee) ee MMM (8.8 eM) eee eeeeeee ee ee eee 8 eee eee eeeeeee eeee MMM (8.8 eM). Me eeeeeee eeeeeeeee 888 (8.88 eeee, 8.8 eeeee) ee MMM (8.8 eM) eee e eeee ee 8-[eeeeeeee(eeeeee)eeeee]-8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee (88; 888 ee, 8.888 eeee, 8.88 eeeee) ee MMM (8.8 eM) eeee eeeeeeeeeeee eeeee, eee eee eeeeeee eee eeeeeeeeee ee −88 °M eee 88 e. Meeee eeeeeeee eeee Me8M, eee eeeeeee eee eeeeee eeeeeee e eee ee eeeeee eee, eeeeeee eeee MeMMe. Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeee MMM (eeeeee/MM8Me8 88:8) ee eeeeee eeeeeee eeeeeee 888 eee 888 ee e eeeeeee ee eeeeeeeeeeee.

References


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