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1.1.10.2.1 Cyanation Using Silyl Cyanides

DOI: 10.1055/sos-SD-212-00203

Goldfuss, B.Science of Synthesis: C-1 Building Blocks in Organic Synthesis, (20141367.

The first catalytic asymmetric 1,4-additions of cyanide to α,β-unsaturated carbonyl compounds were reported by Jacobsen and co-workers in 2003.[‌81‌] Under the optimized conditions, aluminum–salen catalyst 40 promotes the conjugate addition of hydrogen cyanide, generated in situ from trimethylsilyl cyanide and propan-2-ol, to a range of β-alkyl α,β-unsaturated imides 39 to give products 41 with high yields and enantiomeric excesses (Scheme 43). The steric bulk of the β-substituent (R1) of the imides 39 has little effect on the enantioselectivity of the reactions but does effect the reactivity of the substrate; imides with bulkier substituents require higher catalyst loading and reaction temperature to achieve full conversion.

Meeeee 88 Meeeeeeeʼe Meeeeeeee Meeeeeeee ee α,β-Meeeeeeeeee Meeeee[‌88‌]

Meeeeeeeeee 88

M8 88 (Meeee) MMMMM (Meeee) eMeMM (Meeee) Meee (°M) Meee (e) ee (%) Meeee (%) Mee
Me 8.88 8.8 8.8 88 88 88 88 [‌88‌]
Me 8.88 8.8 8.8 88 88 88 88 [‌88‌]
Me 8.88 8.8 8.8 88 88 88 88 [‌88‌]
eMe 8.88 8.8 8.8 88 88 88 88 [‌88‌]
eMe 8.88 8.8 8.8 88 88 88 88 [‌88‌]
(MM8)8MM=MM8 8.88 8.8 8.8 88 88 88 88 [‌88‌]
e-Me 8.88 8.8 8.8 88 88 88 88 [‌88‌]
MM8MMe 8.88 8.8 8.8 88 88 88 88 [‌88‌]

Me e eeeeeee eeeeeeeeeee ee eeee eeee, ee eee eeeee eeee eeeeeeeeeee eeee eeeeeeeee ee eeeeeee eeeeeeee–eeeee eeeeeee 88 eee eeeeee–eeeee eeeeeee 88 eeeeeeee eeeeeeee eeeeeee ee eee eeeeeeeee eeeeeeeee ee α,β-eeeeeeeeeee eeeeee (Meeeee 88).[‌88‌] Meeeeeeeee, eee eee ee eeeeee eeeeeee 88 ee 88 eeeee eeeeeeee eeee eeee eeeeeeeeee, eee ee eeeeeeeeeee eee eee eeeeeeeee eeeeeee eeeeeeee eeeeeeee ee eeeeeeeeeeeee eeeeeee eeeeeeee eeeee eeee eeee eee eeeeeeee 88 eeeeeeeee eeeee, eeeeeee eeeee eeeeeeee eeeeeee eee eee eee ee eeee 8 eeeeeeeeeee ee eeeeeeeeeeeeee eeeeeee. Meeeeeeeeee, eee eeeeeeeee eee eeeeeee eeeeeeee ee eeee eeeeeeeeeee.

Meeeee 88 Meeeeeeeeee Meee Meeeeeeee eee Meeeeeeee Meeeeeeee ee α,β-Meeeeeeeeee Meeeee[‌88‌]

Meeeeeeeeee 88

M8 Meee (e) ee (%) Meeee (%) Mee
Me 88 88 88 [‌88‌]
Me 8 88 88 [‌88‌]
Me 8 88 88 [‌88‌]
eMe 8 88 88 [‌88‌]
eMe 8 88 88 [‌88‌]
(MM8)8MM=MM8 88 88 88 [‌88‌]
e-Me 88 88 88 [‌88‌]
MM8MMe 88 88 88 [‌88‌]

Me 8888, Meeeeeeee eee ee-eeeeeee eeeeeeeee ee eeeeeeeeeeeeeeee eeeeeeeee eeeeeeeee ee α,β-eeeeeeeeeee 8-eeeeeeeeeeee 88 eeeeeeeee ee eeeeeeeeee(MMM) eeeeeeeeeeee ee eee eeeeeeee ee eeeeee eeeeee 88.[‌88‌] Meeee eeeee eeeeeeeeee, eeee β-eeee eeeeeeeeee 88 (M8 = eeee) eee α,β-eeeeeeeeeeeee eeeeeeeeee 88 (M8 ≠ M), eeeee eeee eeeee Meeeeeeeʼe eeeeeeeeee (eee eeeee), eee eeeeeeeeeeee eeeeeeee eeee eeee eeeeeeeeeeeeeeeeee, eeeeee eeee eeee eeeeeeee eeeee (Meeeee 88).

Meeeee 88 Meeeeeeeeʼe Meeeeeeee Meeeeeeee ee α,β-Meeeeeeeeee 8-Meeeeeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Me(MeMe)8/88 (eee%) MMMMM (Meeee) Meee (e) ee (%) Meeee (%) Mee
Me M 88 8 88 88 88 [‌88‌]
8-MeMM8M8 M 88 8 88 88 88 [‌88‌]
8-e-MeM8M8 M 88 8 88 88 88 [‌88‌]
(MM8)8Me M 8 8.8 88 88 88 [‌88‌]
Me M 8 8.8 88 88 88 [‌88‌]
eMe M 8 8.8 88 88 88 [‌88‌]
e-Me M 8 8.8 88 88 88 [‌88‌]
eeeeeeee-8-eeee M 88 8 888 88 88 [‌88‌]
(MM8)8 8 8 8e e 88 [‌88‌]

e Meeeeeee eeeeeee eee ee eeee eeeeeeeeeee.

e ee ee (8M,8M)-eeeee-eeeeee = 88%; ee ee (8M,8M)-eee-eeeeee = 88%; eeeee (eeeee/eee) 8.8:8.

Meeeeeee ee eee eeeeeeee eeee ee eee eeeeeeeeee eeeeeeeee eeeeeeee eee ee eeeeee 88, eeeee eeeeeeee eeeeeee eeeeeeee eeeee eee, ee eeeeeee eeeee, eeeeeeee eeeeeeee eeeeee ee eeeeeeee 88 eeeeeeee ee eee eeeeeee eeeeeee eeeeee 88 (Meeeee 88).[‌88‌] Meeeeeeeeeeee, eee ee eeeeee 88 eeeee ee eeeeeeeeeeeeeeee eeeeeeee eeeeeeee eeeeeeee eeee eee eeeeeeeeeeeee eeeeeeee ee eeeee eeeeeeeee ee eee eeeeeeee ee eeeeee 88; eeee ee eee ee eeeeeeeeeee ee eee eeeeee-eeeee eeeeeeeee eeeeeeeee ee eee eee eeeeeeeee eeeeeeeee.[‌88‌]

Meeeee 88 Meeeeeeee Meeeeeeee ee 8-Meeeeeeeeeee Meeee e Meeeee Meeeee Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Me(MeMe)8 (eee%) Meeeee 88 (eee%) Meee (e) ee (%) Meeee (%) Mee
eMe M 8 8.8 8.8 88 88 [‌88‌]
eMe M 8 8 88 88 88 [‌88‌]
Me M 8 8.8 8.8 88 88 [‌88‌]
e-Me M 8 8.8 8.8 88 88 [‌88‌]
(MM8)8Me M 8 8.8 88 88 88 [‌88‌]
Me M 8 8.8 88 88 88 [‌88‌]
8-e-MeM8M8 M 88 88 88 88 88 [‌88‌]
(MM8)8 8 8.8 8 e 88 [‌88‌]

e Meeee eeeeeeeeeeee: 88% ee; eeeee eeeeeeeeeeee: 88% ee; ee 8.8:8.

Meeeeeeee eee ee-eeeeeee eeee eeee eeeeeee eeeeeee 88 eee 88 ee eee eeeeeeeeee eeeeeeeee ee eeeeee.[‌88‌] Meeee eee eeeeeeeee eeeeeeeeee, eeeee eee eeee-eeeeeeeeeeeeeeeeee eeeeeee ee eee eeeeeee eeeeee, eeeeeee 88 eee 88 eeee eeeeeee eeeeeeeee 8,8-eeeeeeeee ee eeeeee ee eeee eeeeeeee 88 eeee eeee eeeeeeeeeeee eeeeee; ee eeeeeeee ee 8,8-eeeeeeee ee eeeeeee eee eeeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeeeʼe Meeeeeeee Meeeeeeee ee Meeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 Meeeee Me(MeMe)8 (eee%) Meee (°M) Meee (e) ee (%) Meeee (%) Mee
Me M Me 88 (88 eee%) 88 −88 88 88 88 [‌88‌]
Me M Me 88 (8.8 eee%) 8 −88 88 88 88 [‌88‌]
Me M eMe 88 (88 eee%) 88 8 88 88 88 [‌88‌]
Me M eMe 88 (8.8 eee%) 8 8 88 88 88 [‌88‌]
Me M Me 88 (88 eee%) 88 ee 88 88 88 [‌88‌]
Me M Me 88 (8.8 eee%) 8 ee 88 88 88 [‌88‌]
Me M (MM8)8Me 88 (88 eee%) 88 −88 88 88 888 [‌88‌]
Me M Me 88 (88 eee%) 88 −88 88 88 888 [‌88‌]
(MM8)8Me M Me 88 (88 eee%) 88 −88 88 88 88 [‌88‌]
Me M Me 88 (88 eee%) 88 8 8 88 88 [‌88‌]
(MM8)8 Me 88 (88 eee%) 88 8 88 88e 88e [‌88‌]

e ee ee eee-eeeeee; eeeee (eee/eeeee) 8.8:8.

e Meeeeeee eeeee ee eee- eee eeeee-eeeeeee.

Meeeeeeeeee 88M

e MMMMMMM (Meeee) Meee (e) ee (%) Meeee (%) Mee
8 8.8 8 88 88 [‌88‌]
8 8 88 88 88 [‌88‌]
8 8 88 88 88 [‌88‌]

Meeeeeeee eee ee-eeeeeee eeee eeee eeeeeeeee eeeeee 88, eeeee eeeeeeeeeeee eeeeeeee eee eeeeeeeee 8,8-eeeeeeeee ee e eeeee ee β,β-eeeeeeeeeeeee α,β-eeeeeeeeeee eeeeeee eee 8-eeeeeeeeeeee, eeeeeee eeeeeeeeee eeeeee eeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee Meeeeeeee Me Meee Meeeeeeeee Meeeee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 M8 Meee (°M) Meee (e) Meeeeee Meeeeee ee (%) Meeee (%) Mee
eMe Me M Me ee 88 M 88 888 [‌88‌]
Me eMe M Me ee 88 M 88 888 [‌88‌]
Me Me M Me ee 88 (+) 88 88 [‌88‌]
Me Me M Me ee 88 (−) 88 88 [‌88‌]
eMe Me M Me 88 88 M 88 88 [‌88‌]
Me eMe M Me 88 8 M 88 888 [‌88‌]
Me Me M (MM8)8Me 88 8 (+) 88 88 [‌88‌]
Me Me M (MM8)8Me 88 8 (−) 88 88 [‌88‌]
Me Me M Me 88 8 (+) 88 888 [‌88‌]
Me Me M Me 88 8 (−) 88 888 [‌88‌]
Me Me M Me 88 88 e.e. 88 88 [‌88‌]
Me Me M Me 88 88 e.e. 88 888 [‌88‌]
Me Me M Me 88 88 (−) 88 88 [‌88‌]
Me Me M Me 88 8 (+) 88 88 [‌88‌]
Me (MM8)8 Me 88 8 e.e. 88e 88e [‌88‌]
Me Me M eeeeee-8-ee 88 88 (−) 88 888 [‌88‌]
Me Me M eeeeee-8-ee 88 88 (+) 88 88e [‌88‌]
eMe Me M eeeeee-8-ee 88 88 M 88 888 [‌88‌]
Me eMe M eeeeee-8-ee 88 88 M 88 88 [‌88‌]
Me Me M eeeeee-8-ee 88 88 (+) 88 88e [‌88‌]
Me Me M eeeeee-8-ee 88 88 (−) 88 888e [‌88‌]

e e.e. = eee eeeeeeee.

e Meeeeeeeee ee MMM.

e Meeee ee eee (eeeee) eeeeee; ee 88:8.

e 8.88 eee% 88 eee 8.8 eee% Me(MeMe)8 eeee eeee.

e 88 eee% 88 eee 88 eee% Me(MeMe)8 eeee eeee.

Meee eee ee-eeeeeee eeee eeeeeeee eeeeeee-eeeeeeeee eeeeeeee–eeeee eeeeeeee 88 eee eeeeeeeeee eeeeeeeee eeeeeeeee ee α,β-eeeeeeeeeee eeeeee (Meeeee 88).[‌88‌] Meee eeeeeeee eeee eee eeeeeeeee eeeeeeee eeeeeeee eeeeeeeee eeeeeeee eeeeeeee ee eee eeeeeeeee eeeeeeeeeee eeeeeeeee, eee eeeeeeee eeee eeeeee eee eeeeeeeeeeeeeeeeee eeee e eeeeeeeee eeeeeeee eeeeeee ee 8–88 eee%. Mee eeeeeeee 88 eee ee eeeeee eeeeeeeee eeee eee eeeeeeee eeeeeee eeeee eee eeeeeeee, eee eee ee eeeeee eeee eeeee eeeeeee eeeeeeeeeee eeee ee eeeeeeee.

Meeeee 88 Meeeeeeee Meeeeeeee Meeeeeeee ee e Meeeeee-Meeeeeeee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 ee (%) Meeee (%) Mee
Me 88 88 [‌88‌]
Me 88 88 [‌88‌]
eMe 88 88 [‌88‌]
(MM8)8Me 88 88 [‌88‌]
e-Me 88 88 [‌88‌]

Meee eee ee-eeeeeee eeee eeeeeeee ee eeeeeeeeee eeeeeeeee ee eeeeeeeeeeee eeeeeeeee ee e eeeeeeee–eeeee eeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeee–Meeee Meeeeeeee Meeeeeeeee Meeeeeeee Meeeeeeee ee Meeeeeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meee (e) Meeee (%) ee (%) Mee
eMe M 8 88 88 [‌88‌]
Me M 8 88 88 [‌88‌]
Me M 8 88 88 [‌88‌]
MM(MMe)8 M 88 88 88 [‌88‌]
(MM8)8MMMMMM M 8 88 88 [‌88‌]
(MM8)8MMMMMM M 88 88 88 [‌88‌]
(MM8)8 88 88 e [‌88‌]

e eeeee-Meeeee 88% ee; eee-eeeeee 88% ee; eeeee (eeeee/eee) 88:88.

Meeeeeeeeeee Meeeeeeee

M-(8-Meeeeeeeeeeee)eeeeeeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeeeeeeeeee eeeeeee eee eee eeeeeeeeee eeeeeeee eee eeeeeeeee eeeee.

Meeeeeee eeeeeee 88 (88.8 ee, 8.8 eeee) eee eee eeeee 88 (8 eeee) eeee eeeeeeee ee e 88-eM Meeeeee eeeee eeeee M8. Meeeeee (8.8 eM) eee MMMMM (888 µM, 8.8 eeee) eeee eeeee ee eeeeeee, eee eee eeeeeee eee eeeeee eeeeee eeeee eee eeeeee eeee eeeeee eeeeeeeeeee. Mee eeeeeeee eeeee eee eeee eeeeee ee e eeeee eeee ee eeeeeee eeeeeeeeeee, eee eMeMM (888 µM, 8.8 eeee) eee eeeee eeeeeeee eeee 8 eee. Mee eeeeee eee eeeeee, eee eee eeeeeee eee eeeeeee eee eee eeeeeeeee eeeeee ee eeee. Meeeeeee eeee eeeeeee eeeee eeeeeee eeeeeeee eeee e M8MM8 eeee eeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee.

(M)-8-Mee-8-eeeeeeeeeeeeeeeeeeee (88, M8 = Me; M8 = M; M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

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

Me e eeee ee eeeeee 88 (8.8 ee, 8.888 eeee) ee MMM (8.8 eM), 8.8 M Me(MeMe)8 ee MMM (88 µM, 8.88 eeee) eee eeeee ee ee. Mee eeeeeee eee eeeeeee ee 88 °M eee 8 e, eee eeee eee eeeeeee eee eeeeeeeeee. Mee eeeeeeeee eeeeeeeeeee eee eeeee eeeee eeeeeee eeeeeeee (<8 Meee) eee 8 e, eee MMM (8.8 eM) eee eeee eeeee. (M)-Meee-8-ee-8-eee (8.88 eeee) eee eeeee ee ee, eee eee eeeeeee eee eeeeeeeeeee eeeeee ee −88 °M. M eeee eeeeeeee ee eeeeee e eeee ee MMMMMMM (88.8 ee, 8.88 eeee) ee MMM (8.8 eM) eee e eeee ee 8,8-eeeeeeeeeeeeee (88.8 ee, 8.8 eeee) ee MMM (8.8 eM) ee ee eee 88 eee eee eeeee ee eee eeeeeee ee −88 °M. Meee, eee eeeeeeeeeee eee eeeeeeeee ee −88 °M. Meeee 88 e, eee eeeeeee eee eeeeee eeeeeee e eeeee eee ee eeeeee eee (eeeeeee eeee MeMMe), eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee (MMMMMMM: MMM eeeeeeeee ee eee eeeeeee ee eeeeee eeeee: eeeee eeeeeeeeee eeeeee ee eeeeeeeee ee e eeee-eeeeeeeeee eeee). Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, Me8M/eeeeee 8:8) ee eeeeee e eeeeeeeee eee; eeeee: 88.8 ee (88%); 88% ee (eeeeeeeeee ee MM).

References


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