Synthesis of 3-Fluoropyrrolidines and 4-Fluoropyrrolidin-2-ones from Allylic Fluorides

被引：12

作者：

Combettes, Lorraine E. ^{[1
]}

Schuler, Marie ^{[1
]}

Patel, Rakesh ^{[1
]}

Bonillo, Baltasar ^{[1
]}

Odell, Barbara ^{[1
]}

Thompson, Amber L. ^{[1
]}

Claridge, Tim D. W. ^{[1
]}

Gouverneur, Veronique ^{[1
]}

机构：

[1] Univ Oxford, Chem Res Lab, Oxford OX1 3TA, England

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2012年 / 18卷 / 41期

基金：

英国工程与自然科学研究理事会;

关键词：

diastereoselectivity; fluorine; iodocyclization; lactams; nitrogen heterocycles; PART I; NATURAL-PRODUCTS; FLUORINATION; PYRROLIDINE; INHIBITOR; STABILITY; POTENT; FLUORODESILYLATION; ISOMERIZATION; INDOLIZIDINE;

D O I：

10.1002/chem.201201576

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Various 3-fluoropyrrolidines and 4-fluoropyrrolidin-2-ones were prepared by 5-exo-trig iodocyclisation from allylic fluorides bearing a pending nitrogen nucleophile. These bench-stable precursors were made accessible upon electrophilic fluorination of the corresponding allylsilanes. The presence of the allylic fluorine substituent induces syn-stereocontrol upon iodocyclisation with diastereomeric ratios ranging from 10:1 to > 20:1 for all N-tosyl-3-fluoropent-4-en-1-amines and amides. The sense and level of stereocontrol is strikingly similar to the corresponding iodocyclisation of structurally related allylic fluorides bearing pending oxygen nucleophiles. These results suggest that the syn selectivity observed upon ring closure involves I2p complexes with the fluorine positioned inside.

引用

页码：13126 / 13132

页数：7

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