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Lipase‐Catalyzed Domino Kinetic Resolution/Intramolecular Diels–Alder Reaction: One‐Pot Synthesis of Optically Active 7‐Oxabicyclo[2.2.1]heptenes from Furfuryl Alcohols and β ‐Substituted Acrylic Acids
Author(s) -
Akai Shuji,
Naka Tadaatsu,
Omura Sohei,
Tanimoto Kouichi,
Imanishi Masashi,
Takebe Yasushi,
Matsugi Masato,
Kita Yasuyuki
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020916)8:18<4255::aid-chem4255>3.0.co;2-6
Subject(s) - kinetic resolution , intramolecular force , diels–alder reaction , domino , catalysis , optically active , lipase , chemistry , organic chemistry , furfuryl alcohol , enantioselective synthesis , enzyme
The first lipase‐catalyzed domino reaction is described in which the acyl moiety formed during the enzymatic kinetic resolution of furfuryl alcohols (±)‐ 3 with a 1‐ethoxyvinyl ester 2 was utilized as a part of the constituent structure for the subsequent Diels–Alder reaction. The preparation of ester 2 from carboxylic acid 1 and the subsequent domino reaction were carried out in a one‐pot reaction. Therefore, this procedure provides a convenient preparation of the optically active 7‐oxabicyclo[2.2.1]heptene derivatives 5 , which has five chiral, non‐racemic carbon centers, from achiral 1 and racemic 3 . The overall efficiency of this process was dependent on the substituent at the C‐3 position of 3 , and the use of the 3‐methylfurfuryl derivatives, (±)‐ 3 b and (±)‐ 3 f , exclusively produced diastereoselectivity with excellent enantioselectivity to give (2 R )‐ syn ‐ 5 (91–≥99 % ee ) and ( S )‐ 3 (96–≥99 % ee ). Similar procedures starting from the 3‐bromofurfuryl alcohols (±)‐ 3 h – j provided the cycloadducts (2 R )‐ syn ‐ 5 j – q (93–≥99 % ee ), in which the bromo group was utilized for the installation of bulky substituents to the 7‐oxabicycloheptene core.