Pseudo-macrocyclic chelation control in remote asymmetric induction. Highly efficient 1,7-asymmetric inductive hydride reduction and Grignard reaction of y-keto esters of 1,1'-binaphthalen-2-ols bearing an appropriate oligoether group as the 2'-substituent

Yasufumi Tamai, Tetsutaro Hattori, Masamitsu Date, Shinji Koike, Yoshinori Kamikubo, Masahiro Akiyama, Kazuhiro Seino, Hideki Takayama, Tomohito Oyama, SotaroMiyano

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22 Citations (Scopus)

Abstract

Highly efficient 1,7-asymmetric induction was achieved in DIBAL-H reduction and Grignard reaction of y-keto esters of podand-type l,l'-binaphthalen-2-ol derivatives bearing an appropriate oligoether group as the 2'-substituent. Thus, the DIBAL-H reduction of keto esters 4 in dichloromethane-toluene at -78 °C in the presence of an excess of MgBr2'OEt2 afforded, after further reduction of the resulting diastereomeric hydroxy esters, 1,4-diol 8 with up to 92% optical yield. A similar treatment of keto esters 4,5 and 7 with Grignard reagents gave the corresponding 4,4-disubstituted butan-4-olides 10-13 with up to 99% optical yield. The complexation experiments of keto ester 4b suggested that the highly efficient 1,7-asymmetric induction originated from the formation of a pseudo-macrocyclic magnesium complex composed of the podand keto ester and MgBr2.

Original languageEnglish
Pages (from-to)1685-1694
Number of pages10
JournalJournal of the Chemical Society - Perkin Transactions 1
Issue number12
DOIs
Publication statusPublished - 1999 Jan 1

ASJC Scopus subject areas

  • Chemistry(all)

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