Adventures in Ring-Contraction Reactions

作者：Silva Luiz F Jr^*

来源：Synlett, 2014, 25(4): 466-476.

DOI：10.1055/s-0033-1340472

• total synthesis
• ring contractions
• oxidative rearrangements
• thallium(III)
• hypervalent iodine

Nearly two decades of work on ring-contraction reactions is discussed in this account. We have developed several reliable protocols for the rearrangement of a number of different substrates using thallium(III) salts and, more recently, hypervalent iodine(III) reagents. A variety of ring systems, such as cyclopentanes, cis- and trans-hydrindanes, and indanes, can be obtained using these methods. Additionally, the stereoselective total syntheses of the sesquiterpenes ()-, (-)- and (+)-mutisianthol and (+)-bakkenolide A, the indole alkaloid ()- and (+)-trans-trikentrin A, and the potential drug ()-indatraline have been achieved through a ring-contraction approach. 1Introduction 2Ring-Contraction Reactions Promoted by Thallium(III) 2.1Thallium(III)-Mediated Ring Contraction of Cyclic Ketones 2.2Thallium(III)-Mediated Ring Contraction of Cyclic Olefins 2.3Thallium(III)-Mediated Ring Contraction of Homoallylic Alcohols 3Ring-Contraction Reactions Promoted by Iodine(III) 4Conclusion

• 出版日期2014-3-3