Forging C–C Bonds with Hindered Nucleophiles and Carbonyl Electrophiles: Reactivity and Selectivity of Allylic Tin Reagents/n-BuLi,Organometallics

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Forging C–C Bonds with Hindered Nucleophiles and Carbonyl Electrophiles: Reactivity and Selectivity of Allylic Tin Reagents/n-BuLi
Organometallics ( IF 2.5 ) Pub Date : 2017-12-07 00:00:00 , DOI: 10.1021/acs.organomet.7b00765
Morgan Cormier ₁ , Maha Ahmad ₁ , Jacques Maddaluno ₁ , Michaël De Paolis ₁

Affiliation

Under activation with n-BuLi, trialkylstannanes containing crotyl-, geranyl-, and phenyldienylmethyl appendages were reacted with efficiency and selectivity to various ketone and enone electrophiles with low reactivity. The straightforward process gives access to tertiary alcohols that are vicinal to quaternary carbons. With α,α′-dimethoxy-γ-pyrone, on the other hand, the grafting of a dienyl side chain was effected to prepare dienyl α′-methoxy-γ-pyrone in a stereo- and regioselective and convergent manner. Furthermore, the advantages of this route were highlighted for the preparation of organolithium species at low temperature with the formation of a minimum amount of salts. Synthetic manipulations were demonstrated to illustrate the potential of the chemistry for constructing acyclic and cyclic terpene scaffolds.

中文翻译：

与受阻的亲核试剂和羰基亲电试剂锻造C–C键：烯丙基锡试剂/ n -BuLi的反应性和选择性

根据与激活ñ-BuLi，含有巴豆基，香叶基和苯基二烯基甲基附件的三烷基锡烷与低反应性的各种酮和烯酮亲电试剂高效且选择性地反应。简单的过程使人们能够获得对季碳不利的叔醇。另一方面，用α，α′-二甲氧基-γ-吡喃酮进行二烯基侧链的接枝以立体和区域选择性和会聚的方式制备二烯基α′-甲氧基-γ-吡喃酮。此外，该路线的优势突出了在低温下制备有机锂物种并形成最少量的盐的优势。已证明合成操作说明了化学方法用于构建无环和环状萜烯支架的潜力。

更新日期：2017-12-07

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