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36.6.1.1.2.1 Variation 1: With Allyl Groups Containing Stereocenters at C1 or C4

DOI: 10.1055/sos-SD-036-00556

Perkins, M. V.Science of Synthesis, (200836690.

Chiral allylstannanes with stereocenters at C1 or C4 prove to be very useful reagents in the stereocontrolled syntheses of homoallylic alcohols, and can show high substrate-driven selectivity in reactions with both achiral and chiral aldehydes.[‌61‌] Early examples of the thermal-mediated reactions of the racemic allylstannane 75 with aldehydes are depicted in Scheme 34.[‌62‌,‌63‌] In such cases the reactions proceed through cyclic chair transition states 77 to give the anti-products 76.

Meeeee 88 Meeeeee Meeeeeeee ee (M)-Meeeeeeeeeeeeee eeee Meeeeeeee[‌88‌,‌88‌]

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

Meeeee 88 Meeeeeeeeee eee Meeeeeeeee Meeeeeeee ee ()-(Meeeeeeeee)eeeeee Meeeee[‌88‌]

Meeeeee eeeeeeeeee ee eee eeeeeeeeeee ee eeeeeeeeeeeeeeee eeeeeeee α-eeeeeeeeeeeeeee eeee eeee eeeeeeee.[‌88‌‌88‌] Me ee eeeeeee ee eee eeeeeeee eeeeeeee eee ee eeeeeee eeee eeeeeeeeeeeeeeeeeeeeee, eeeeeeee ee 8,8-(eeeeeeeeeeeee)eeeeeeeeeeee (MMMM) ee eeee eee eeeeeeee eeeeeeee 88. Meeeeeeeeeeeeeee eeeeeeeee ee eeee eeeeeeee eeee 8,8-eeeeeeeee-8,8-eeeeeeeeeeeeeeeee eeeeeeee eeeeeee (MMMMM-M) eeeee eee M-eeeeeee 88 ee ee eeeeeeeeeeee eeeeee ee 88%. Meeeeeeeee ee eee eeeeeee eeeee ee eeee eeeeeeee eeeee eee eeeeeeeeeeeeeee eeeee 88, eeeee eee ee eeeeeee eeee eeeeeee eeeeeeeee ee eee eeeeeeee ee eeeee eeeeeeeeeeeeeeeeee eeeee eeeeeee ee eeeee ee Meeeee 88.[‌88‌,‌88‌] Meeee eeeeeeeee eeeeeee eeee eeeeeee eeeeeeeee (MM8) eeeeee eee eeeeeeee 88M88M. Mee eeeeeeeeeee eeeeeeee ee eeeeeeeeee eee eee eeeeeeee-eeeee eeeeeeee eeeeeeee eee eee α,β-eeeeeeeeeee eeeeeeee eee-8-eeee, eee eeeeee eeeee eee eee-8-eeee. Meeee eeee eeeeeeeeeee eeeee eee eeee eeeeeeeeeee ee eeeee eeeee ee eeeeee ee eeeee eeee eeeee ee e eeeeee eeeeeeeeeee (eeeeeeeeeeeeeeeee) eeeeeee eee eeeeeeee eeeeeeeeeeeee, eee eeeeeee eeeeeeeeeeee eee eee eeeeee eeee eeeeeeee ee eee eeeeeeee.

Meeeee 88 Meeeeeeeeee eee Meeeeeeeee Meeeeeeee ee {(8M,8M)-8-[(Meeeeeeee)eeeeeee]eeee-8-ee-8-ee}(eeeeeeee)eeeeeeee[‌88‌,‌88‌]

Meeeeeeeeee 88

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

Mee eeeeeeeee ee eee eee eeeee eee-eeeeeee eeeeeeee 88M eee 88M ee eeeeeeeeeeee ee eeeeeeeeeeeee ee eee eeeeeeeeee eeeeee 88M eee 88M ee eeeee eee eeeeeeeeeeeeee eeeeeeeeeee ee eee M=M eeee eeeeeeeee eee eeeeee eeeeeeeeeeee eeeeeee eee eeeeeeee eee eee eeeeeeee eeeeeeeeeeee eeeee eee M8 (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeeee Meeeee eee eee Meeeeeeee eeeeeee {(8M,8M)-8-[(Meeeeeeee)eeeeeee]eeee-8-ee-8-ee}(eeeeeeee)eeeeeeee eee Meeeeeeee ee eee Meeeeeee ee Meeee Meeeeeeeeee[‌88‌]

Me eee eeeeeee ee e eeeeeeee eeeeeeee, α-eeeeeeeeeee eeeeeeeeeeeeee ee eee eeee 88 eeeeeee eeeeeeeeeeeee ee Meeee eeeee, eeee ee eeeee eeeeeeeeeeeeeeeeee eeeee eeeeeee ee eeee-eeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeeeeeeeee, ee eee M-γ-eeeeeeeeeee eeeeeeeeeeeeee. Meeee eeeeeee eeee eeeee eeee eeeeeeeee ee eee eeeeeeee ee eeeeeee Meeee eeeee ee eeee eeeeee eee eee-eeeeeeeeeeeee 8,8-eeeeeeeeeeeeee eeeeeee. Me eeeeeeeeeee ee eeee eeee ee eeeeeeeeeeeee eee eeeeeeee ee eeeeeeeeeee ee Meeeee 88; ee ee eeeeeeee ee eee eeeeeeeee ee eee eeeee eeeeeeeee ee eee eeeee eeee eeeeeeeee ()-eeeeeeeeee.[‌88‌] Meee, eee eeeeeee eeeeeeee, eeeeeee eeee eeee-8-eeee eee eeeeeeeeeeeeeeeeeeeeee, ee eeeeeee eeee 8,8-(eeeeeeeeeeeee)eeeeeeeeeeee (MMMM) eeeeee eee eeeeeeee eeeeeeee 88. Meeeeeeeeeeeeeee eeeeeeeee eeee 8,8-eeeeeeeee-8,8-eeeeeeeeeeeeeeeee eeeeeeee eeeeeee eeeee eee eeeeeee 88 eeee ee eeeeeeeeeeee eeeeee ee eeeeeee eeee 88%. Meeeeeeee eeee eeee-eeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeeeeeeeee eeeeeeee eee eeeeeee eee eeeeee e eeeeeeeeeeeee ee eee M-γ-eeeeeeeeeee eeeeeeeeeeeee 88. Meee eeee eeeeeeee ee eeeeeee eeee (8M)-8-eeeeeeeeee-8-eeee eee eeeee eeeeeeeeeeeeeeeeee eeeee eeeeeee ee eeeeeee eee eeeeee 88 ee 88% eeeee eee ee 88% ee.

Meeeee 88 Meeeeeeeeee eee Meeeeeeeee Meeeeeeee ee e M-γ-Meeeeeeeeee Meeeeeeeeeeee[‌88‌]

Mee 8-eeeeeeeeeeeeee eeeeeeeeeeeee 88 eeeeeeeee eeeeeeeeeeeeeee/eeeeeeeeeeeee eeee eeeeeee eeee eee(MM) eeeeeeee ee 88°M (Meeeee 88).[‌88‌,‌88‌] Mee eeeeeeeeeeee 88 eeee ee eeeeee eeeeee eeee eeeeeeeee ee eeee eee 8,8-eee-eeeeeeee eee-88 ee eeee eeeeee.[‌88‌,‌88‌] Mee eeee eeeee ee eeeeeeeeeeeeeee eeeeeeee eee eeeee eeeeeeeee eee ee eeeeeeeeeeee ee eee eeeee eeeeeeeeee eeeeee 88. Meeee eeeeeeeeee eeeeee eeeeeee eeeeeeeeeeee ee eee eeeeeeeee eeeee ee eee eeeeeeee-eeeeeeeee eeeeeeeeeeeeeeee eeee.

Meeeee 88 Meeeeeeeeeeee eee Meeeeeeee ee e 8-Meeeeeeeeeeeee Meeeeeeeeeeee[‌88‌,‌88‌]

Meeeeeeeeeee Meeeeeeee

(8M,8M)-8-(eeee-Meeeeeeeeeeeeeeeeee)-8-(eeeeeeeeeeeeeee)eeeee-8-eee (88):[‌88‌]

MMMMMMM: Meeee eeeeeee eeeeeeee eeeeeee eeeeee eeeeeeeeee eeee e eeeeeee ee eeeeeeeeee, eee eee eeeeee ee eeeeeee ee eeeeeeee eeeeeeee.

eMe8MM (8.88eM, 88.8eeee) ee eeeee MMM (88eM) eee eeeeee ee 8°M eee 8.8M MeMe ee eeeeee (8.88eM, 88.8eeee) eee eeeee, eeeeeeee eeeee 88eee ee Me8MeM (8.88eM, 88.8eeee). Mee eeeeeeeee eeeeee eeee eee eeeeeee eee 88eee, eeeeee eeeee eeeeee ee 88°M, eee eeeee-8-eeee (8.88e, 88.8eeee) eee eeeee, eeeeeeee, eeeee 88eee, ee 8,8-(eeeeeeeeeeeee)eeeeeeeeeeee (MMMM; 8.88e, 88.8eeee). Mee eeeeeeeee eeee eee eeeeeee eee eeeeee ee 8°M, eee eeeeeee eee 8e. Mee eeeeeeee eee eeee eeeeeeee eeee 8M MM8Me eee eee eeeeeee eee eeeeeeeee eeee Me8M. Mee eeeeeee eeeeeeee eeee eeeeeeee eee eeeee (MeMM8), eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Meeeee eee eeeee ee eee eeeeee eeeeeee eee eee eeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeee eee eeeeee ee MMM. Mee eeeeeeee eeeeeeee 88 eee eeeeeeee ee eeeeee eeeeee ee eeeeeeeeeee eeeeeeee 8,8-(eeeeeeeeeeeee)eeeeeeeeeeee eee eee eeeee eee eeeeeee ee eeeeee eeeeeeeeee. Mee eeeeeeee eee eeeeeeeeeeee ee eeeeeee eee eeeeeeee eeeeeeee (eeeeeee, eeeeeee ee eee eeeeeeee ee eeee eeeeeee ee ee eeeeeeeee ee eeee e eeeeeee eeeeeeee eeee ee MMMMM-M ee 88°M eeeee eee eee eeeeeeeeee eeeeeeeee. Meee ee eeee eeeeeeee ee eeeeeeee eee eeeeeeeee eeeeeeeee eee MMMMM-M eeee eeeee ee eee eeeeeeee eeeeeeee eeeeeeee). MeMeM8 eeeeee (8.88e, 88.8eeee) eee eeeeeeeee ee MMM (88eM). Meee e eeeeee ee 88eee, e eeee ee MeMM (8.88e, 88.8eeee) ee MMM (8eM) eee eeeee eeee eeeeeeee eeeeeeeee ee M8, eeeee eeeee (M)-8,8-eeeeeeeeeeeee-8,8-eeee (8.88e, 88.8eeee) ee MMM (88eM) eee eeeee ee eeeee ee e eeeeeee eeee 8e. Mee eeeeeeeee eeeeee, eeeee eeee eee eeeeeeee eee 8e, eeeeeee ee eeee ee ee, eee eeee eeeeee ee 88°M, eeeeee eee eeeeeeee eeeeeeee ee MMM (88eM) eee eeeee ee eeeee ee e eeeeeee eeee 8.8e. Meeee eeeeeeee eee 88e ee 88°M, eee eeee eee eeeeeeee eeee 8M MM8Me (888eM) eeee 8.8e eeeee eeeee eeee ee 88°M. Mee eeee eee eeee eeeeeee ee eeee ee ee, eeeeee ee eee eeeeeee eeee M8M eee Me8M. Mee eeeeee eeee eeeeeeeee, eee eee eeeeeee eeeee eee eeeeeee eeee 8M MMe, eee eeeeeeeee eeee Me8M. Mee eeeeeee eeeeeeee eeee eeeeeeee, eeeee (MeMM8), eee eeeeeeee, eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeeee eeeeeeeeeeee eeeeeeee (e eeeeee eee) eee 8,8-eeeeeeeeeeeee-8,8-eeee eeee eeeeeeeeee eeee eeeeee (8 ×). Mee eeeeeeeeee eee eeeeeeeee ee eeeeeeeeee, eee eee eeeeee eeeeeeee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeee eee eeeee eeeeeeeeeeee eeeeeeee. Mee eeeeeeeeeeee eeeeeeee eee eeeeeeeeeee ee MM8Me8 eee eeeeee ee 8°M. eMe8MMe (8.8eM, 88.8eeee) eee eeeee, eeeeeeee ee MMMMMMMe (8.88eM, 88.8eeee), eee eee eeeeeee eee eeeeeee eeeeeeeee ee eeeeee eeeeeeee eeeeeeeeeeeee. Mee eeeeeeee eee eeee eeeeeeee eeee eee. ee MeMMM8, eee eee eeeeeee eeeee eee eeeeeeeee eeee MM8Me8 (8 ×). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeee (Me8MM8), eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee); eeeee: 8.8e (88%).

(8M,8M,8M,8M)-8-(eeee-Meeeeeeeeeeeeeeeeee)-8-eeeeeeeeeeeeee-8,8-eeee-8-ee (88):[‌88‌]

M eeee ee eee eeeeeeee 88 (888ee, 8.88eeee) eee 8-eeeeeeeeee-8-eeee (88ee, 8.88eeee) ee MM8Me8 eee eeeeee ee 88°M, eee MM8MMe8 (88 μM, 8.88eeee) eee eeeee. Mee eeeeeee eee eeeeeee eee 8.8e, eee ee eee eeeeeeee eee eee eeee eeeeeee eeeeeeee (MMM), eeeeeeeeee MM8MMe8 (888 μM, 8.88eeee) eee eeeee. Meeee 8e, eee eeeeeeee eee eeeeeeee ee eee eeeeeeee ee eee. ee MeMMM8, eee eee eeeeeee eeeee eee eeeeeeeee eeee MM8Me8 (8 ×). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeee (Me8MM8), eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 8: 888); eeeee: 888ee (88%).

References


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