Highly Substrate-Selective Macrocyclic Ring Closing Metathesis

Ravindra S. Phatake, Noy B. Nechmad, Ofer Reany, N. Gabriel Lemcoff

نتاج البحث: نشر في مجلةمقالةمراجعة النظراء


A selective ring-closing metathesis (RCM) reaction for the formation of large macrocycles by using latent sulfur chelated ruthenium iodide benzylidenes, readily activated by thermal and photochemical (UV-A and visible light) stimuli, is reported. For dienes having one terminal alkene and one internal double bond, the specific affinity of diiodo ruthenium alkylidenes for the unhindered terminus, combined with their reluctance to react with internal olefins, favors RCM over oligomerization, providing high macrocyclic yields even at relatively high concentrations. Alternatively, for substrates containing two internal double bonds, a sacrificial methylene donor can be used to obtain the desired products. With this methodology, lactones, lactams, and macrocyclic ketones ranging from 13- to 22-membered rings could be synthesized in moderate to high yields. In addition, synthetic applications for a one-pot cyclization/reduction sequence to produce Exaltolide, a natural macrolide (commercial musk), Dihydrocivetone, and other saturated macrocycles have been explored. Thus, we disclose herein an important advantage for diiodo ruthenium benzylidene catalysts over their less selective dichloro counterparts and provide a more profound understanding of the mechanisms that provide the enhanced cyclization outcome.

اللغة الأصليةالإنجليزيّة
دوريةAdvanced Synthesis and Catalysis
تاريخ مبكر على الإنترنت2 مارس 2022
المعرِّفات الرقمية للأشياء
حالة النشرنَشْر مسبق في الإنترنت - 2 مارس 2022

ملاحظة ببليوغرافية

Funding Information:
This work was supported by the grants of the Israel Science Foundation (ISF grant no. 506/18) and the Israel Innovation Authority (grant no. 76763).

Publisher Copyright:
© 2022 The Authors.


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