Unknown

Dataset Information

0

Widely applicable synthesis of enantiomerically pure tertiary alkyl-containing 1-alkanols by zirconium-catalyzed asymmetric carboalumination of alkenes and palladium- or copper-catalyzed cross-coupling.


ABSTRACT: A highly enantioselective and widely applicable method for the synthesis of various chiral 2-alkyl-1-alkanols, especially those of feeble chirality, has been developed. It consists of zirconium-catalyzed asymmetric carboalumination of alkenes (ZACA), lipase-catalyzed acetylation, and palladium- or copper-catalyzed cross-coupling. By virtue of the high selectivity factor (E) associated with iodine, either (S)- or (R)-enantiomer of 3-iodo-2-alkyl-1-alkanols (1), prepared by ZACA reaction of allyl alcohol, can be readily purified to the level of ?99% ee by lipase-catalyzed acetylation. A variety of chiral tertiary alkyl-containing alcohols, including those that have been otherwise difficult to prepare, can now be synthesized in high enantiomeric purity by Pd- or Cu-catalyzed cross-coupling of (S)-1 or (R)-2 for introduction of various primary, secondary, and tertiary carbon groups with retention of all carbon skeletal features. These chiral tertiary alkyl-containing alcohols can be further converted into the corresponding acids with full retention of the stereochemistry. The synthetic utility of this method has been demonstrated in the highly enantioselective (?99% ee) and efficient syntheses of (R)-2-methyl-1-butanol and (R)- and (S)-arundic acids.

SUBMITTER: Xu S 

PROVIDER: S-EPMC3891662 | biostudies-literature | 2013 Aug

REPOSITORIES: biostudies-literature

altmetric image

Publications

Widely applicable synthesis of enantiomerically pure tertiary alkyl-containing 1-alkanols by zirconium-catalyzed asymmetric carboalumination of alkenes and palladium- or copper-catalyzed cross-coupling.

Xu Shiqing S   Lee Ching-Tien CT   Wang Guangwei G   Negishi Ei-ichi E  

Chemistry, an Asian journal 20130513 8


A highly enantioselective and widely applicable method for the synthesis of various chiral 2-alkyl-1-alkanols, especially those of feeble chirality, has been developed. It consists of zirconium-catalyzed asymmetric carboalumination of alkenes (ZACA), lipase-catalyzed acetylation, and palladium- or copper-catalyzed cross-coupling. By virtue of the high selectivity factor (E) associated with iodine, either (S)- or (R)-enantiomer of 3-iodo-2-alkyl-1-alkanols (1), prepared by ZACA reaction of allyl  ...[more]

Similar Datasets

| S-EPMC4060698 | biostudies-literature
| S-EPMC5742534 | biostudies-literature
| S-EPMC5359471 | biostudies-literature
| S-EPMC3891660 | biostudies-literature
| S-EPMC7496309 | biostudies-literature
| S-EPMC7541770 | biostudies-literature
| S-EPMC7304281 | biostudies-literature
| S-EPMC2774748 | biostudies-literature
| S-EPMC5632513 | biostudies-literature
| S-EPMC4770434 | biostudies-other