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4.4.10.B Applications of Product Subclass 10 in Organic Synthesis

DOI: 10.1055/sos-SD-004-00260

Singer, R. D.Science of Synthesis, (20024231.

Triorganosilylcopper(I) reagents have been shown to undergo reactions with a wide variety of unsaturated organic substrates to afford products containing new SiC bonds. Appropriate attention to the copper(I) salt from which the cuprate is derived must be given since this factor can influence both chemical yield and regiochemistry of several reactions involving these reagents.[‌20‌] The use of dilithium cyanobis(dimethylphenylsilyl)cuprate, dilithium cyanobis(trimethylsilyl)cuprate, and lithium bis(dimethylphenylsilyl)cupratelithium halides [(PhMe2Si)2CuLiLiX, X=Br, I] has been most widely reported in the literature. These reagents react well with alkynes,[‌8‌] a variety of Michael acceptors[‌8‌] (e.g., α,β-unsaturated esters, ketones, amides, alk-2-enenitriles, etc.), allenes, allylic acetates[‌6‌], acid chlorides,[‌24‌,‌25‌] and 1,3-dienes.[‌21‌]

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Meeeee 8 Meeeeeeee ee Meeeeeeeeeeeeeeeeeee Meeeeeee eeee Meeeeeeeee Meeeeeeee[‌8‌,‌88‌,‌88‌]

Meeeeeeeeee 8

Me M8 M8 Meeeeeeeee Meeee (8/8/8) Meeee (%) Mee
MM Me M 8°M, 88eee 8:8:8 88 [‌8‌]
MM Me M 8°M, 88eee 8:8:8 88 [‌8‌]
MM Me M 88°M, 88eee 8:8:8 88 [‌8‌]
MM Me Me 88°M, 88eee e 88 [‌8‌]
MM MM8Me-Me M 88°M, 8e 8:88:88 888 [‌88‌]
8°M, 8e 8:88:88 88 [‌88‌]
MM MM8MMe M 88°M, 8e 8:8:8 88 [‌88‌]
MM MM8Me Me MMM, MMMM, 88°M 8:8:8 88 [‌88‌]
MM M 88°M 8:8:8 88 [‌88‌]
Me M 88°M 8:8.8:8 88 [‌88‌]
M M 88°M 8:8:8 88 [‌88‌]
MM (MM8)8Me MM8MM 88°M ee ee, 88e 8:8:8 88 [‌88‌]

e MeM88=MeMe8Me ee eeee eeee, eeee eeee ee eeeeeeee ee eeeeeeeeee eeee eeeee MeM88 eeeeee.

e 8=8; eee eeee eeeeeeee.

Meeeee eee eeeee eeeeeee eeee eeeee eeee eeeeeeeeeeeeeeeeeeee(M) eeeeeeee ee eeee eeeeeeeeeeee eee eeeeeeeeee eeeeeeeeeee eeeeeeee (Meeeee 8).[‌88‌,‌88‌] Mee eeeeeeee ee eeeeeeeee eeeeeeee(eeeeeeeeeeeeeeeeeee)eeeeeee eeee eeeeee eeeeeee eeeeeeeeeeee eee ee eee e eeeeeeeeeee eeeeeeeee eeeeeeee. Meeeeeeeeeeee, eee eeeeeeee ee eeeeeee eeeee(eeeeeeeeeeeeeeeeeee)eeeeeee, eeeeeeee eeee eee eeeeeeee ee 8 eeeeeeeeee ee eeeeeeeeeeeeeeeeeeeeeeeeee eeee 8 eeeeeeeeee ee eeeeee(M) eeeeeee, eeee eeeeee ee eeeeeeeeeee eeeeeeeee eeeeee eeeeeeeeeeee ee 88°M eee eeeeeeeeeeee ee 8°M.[‌88‌] Meeeeeeeeeee (eee Meeeeee 8.8.88) eee eeee ee eeeeeeee eee eee eeeeeeee ee eeeeeee eeeeeeee eeee eeeeeeeeeeeeeeeeeeee(M) eeeeeeee (Meeeee 8).[‌8‌]

Meeeee 8 Meeeeeeee ee Meeeeeeeeeeeeeeeeeee Meeeeeee eeee Meeeeee Meeeeeeee[‌8‌,‌88‌‌88‌]

Meeeee 8 Meeeeeeee ee Meeeeeeeeeeeeeeeeeee Meeeeeee eeee Meeeeee Meeeeeee[‌8‌]

Meeeeeeeeee 8

e M8 M8 Meeee (%) Mee
8 M M 88 [‌8‌]
8 Me M 88 [‌8‌]
8 M Me 88 [‌8‌]
8 M M 88 [‌8‌]

Mee eeeeeeeee eeeeeeee ee eeeeeee eee(eeeeeeeeeeeeeeeeeee)eeeeeeeeeeeeee eeeeee [(MeMe8Me)8MeMeMeM] ee α,β-eeeeeeeeeee eeeeeeee eeeeeeeee eeeeeeee eee ee eeeeeee eeee eee ee eeeeeeeeee, eeeeeeeee, ee eeeeeee eeee ee eeeeeeee ee eeee β-eeeeeeeeeeeeee eeeeeeee eeeeeee (Meeeee 8).[‌8‌,‌88‌]

Meeeee 8 Meeeeeeee ee Meeeeeeeeeeeeeeeeeee Meeeeeee eeee α,β-Meeeeeeeeee Meeeeeeee[‌8‌,‌88‌]

Meeeeeeeeee 8

M8 M8 M8 Meeee (%) Mee
M M M 88 [‌8‌]
M Me Me 88 [‌8‌]
M Me MM8Me 88 [‌8‌]
M Me M 88 [‌8‌]
M Me MM8M 88 [‌8‌]
Me Me Me 88 [‌8‌]
Me Me Me 88 [‌8‌]
Me (MM8)8 88 [‌8‌]
M (MM8)8 88 [‌8‌]
M MM8MMMeMM8 88 [‌8‌]
Me MM8MMe8MM8 88 [‌8‌]

Meee eeeeeeeee eeeee eeee eeeeeeeeeeeeeeeeeeee(M) eeeeeeee eeee ee eeeeeeeee eeeeeeee(eeeeeeeeeeeeee)eeeeeee ee eeee eeeeeeeeeee (eee Meeeeee 8.8.88) ee eeeeee ee eeee eeeeee (Meeeee 8).[‌88‌,‌88‌] Meee eeeeeeee eee eeee eeeeeeee ee eee eeeeeeeeeee ee eeeeeeeeeeeeee eeeeeeeeeee eeeeeee eee eee ee eeeeeeeee eeeeeeeeeeeee (eee Meeeeee 8.8.8).[‌88‌] Mee eeeeeeeeeeeeee ee 8,8-eeeeee eeee eeeeeeeeee eeeeeeee ee eee eeeeee eeeeeeeeeeee eeee eeeeeeeeeeeee eeeeeee eee eeee eeee eeeeeeeeeeee (Meeeee 8).[‌88‌]

Meeeee 8 Meeeeeeee ee Meeeeeeeeeeeeeeeeeee Meeeeeee eeee Meee Meeeeeeee[‌88‌,‌88‌]

Meeeee 8 Meeeeeeee ee Meeeeeeeeeeeeeeeeeee Meeeeeee eeee 8,8-Meeeee[‌88‌]

Meeeeeeeeee 8

M8 M8 Meeee (8/8) Meeee (%) Mee
Me M 88:88 88 [‌88‌]
Me Me 88:88 88 [‌88‌]
(MM8)8MM=MMe8 M 88:88 88 [‌88‌]

References