Acid-induced Favorskii-type Reaction: Regiocontrolled Elimination of Acyloin Mesylates Leading to α,β-Unsaturated Ketones and Application to Formal Total Synthesis of (R)-Muscone from Racemic Muscone

被引:2
作者
Ashida, Yuichiro [1 ]
Tanaka, Akihiro [1 ]
Hosomi, Kohei [1 ]
Nakamura, Atsushi [1 ]
Misaki, Tomonori [2 ]
Nakatsuji, Hidefumi [1 ]
Tanabe, Yoo [1 ]
机构
[1] Kwansei Gakuin Univ, Dept Chem, Sch Sci & Technol, 2-1 Gakuen, Sanda, Hyogo 6691337, Japan
[2] Univ Hyogo, Grad Sch Mat Sci, 3-2-1 Kohto, Kamigori, Hyogo 6781297, Japan
来源
CHEMISTRYSELECT | 2016年 / 1卷 / 12期
关键词
synthetic method; rearrangement; elimination; alpha; beta-Unsaturated ketone; muscone; ASYMMETRIC-SYNTHESIS; (-)-(R)-MUSCONE; (R)-(-)-MUSCONE; (+)-(R; Z)-5-MUSCENONE; HYDROGENATION; METATHESIS; CHEMISTRY; POWERFUL;
D O I
10.1002/slct.201600625
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A highly regiocontrolled acid-induced Favorskii-type elimination reaction using unsymmetrically-substituted acyloin mesylates proceeded smoothly to give more substituted alpha,beta-unsaturated ketones under mild conditions. Not only acyclic mesylates but also cyclic acyloin mesylates produced the corresponding higher substituted (thermodynamically stable) alpha,beta-unsaturated ketones via distinctive double-bond-migration pathway. The regioselectivity is nearly exclusive in all 8 examples examined. A plausible fundamental pathway for this regiocontrolled elimination is proposed; (1) isomeric enol and/or cyclopropane formations proceeds to give the cationic inter-mediate and/or the cyclopropane intermediate, respectively, (2) successive crucial step for regioselective MsOH (or H2O) elimination concomitant with specific proton withdrawal leads to the corresponding intermediates, the major E1'-like dienol and the minor E1-like dienol, (3) final tautomerization affords more substituted alpha,beta-unsaturated ketones. Mechanistic speculations for the plausible mechanism and exo/endo selectivity for cyclic acyloin mesylates are also described. The present reaction was applied to a successful synthesis of "chiral" (R)-muscone precursor from readily available "racemic" muscone.
引用
收藏
页码:3215 / 3218
页数:4
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