+ Site Statistics
+ Search Articles
+ PDF Full Text Service
How our service works
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ Translate
+ Recently Requested

All-catalytic, efficient, and asymmetric synthesis of alpha,omega-diheterofunctional reduced polypropionates via "one-pot" Zr-catalyzed asymmetric carboalumination-Pd-catalyzed cross-coupling tandem process



All-catalytic, efficient, and asymmetric synthesis of alpha,omega-diheterofunctional reduced polypropionates via "one-pot" Zr-catalyzed asymmetric carboalumination-Pd-catalyzed cross-coupling tandem process



Journal of the American Chemical Society 127(9): 2838-2839



A highly efficient method for the synthesis of stereochemically pure (>/=99% ee and >50/1 dr) alpha,omega-diheterofunctional reduced polypropionates has been developed. The essential features of the method are represented by the conversion of inexpensive styrene into 2-methyl-4-phenyl-1-pentanol (1) in 50% yield over two steps from styrene via Zr-catalyzed asymmetric carboalumination (ZACA) reaction in the presence of (NMI)2ZrCl2 and Pd-catalyzed vinylation of the in situ generated isoalkylalanes in the presence of Zn(OTf)2 and a catalytic amount of Pd(DPEphos)Cl2. This ZACA-Pd-catalyzed vinylation may be repeated as needed without purification. After the final ZACA reaction, oxidation with O2 provides alpha-hydroxy-omega-phenyl reduced polypropionates, which can be fully or partially purified by chromatography. After acetylation, Ru-catalyzed oxidative cleavage of the Ph ring, and reduction with BH3.THF, the second chromatographic purification provides stereoisomerically pure alpha,omega-diheterofunctional reduced polypropionates (e.g., 9 and 11) that can be further converted to key intermediates 6 and 7 for the synthesis of ionomycin (4) and borrelidin (5), respectively, by known reactions.

Please choose payment method:






(PDF emailed within 0-6 h: $19.90)

Accession: 048207787

Download citation: RISBibTeXText

PMID: 15740104

DOI: 10.1021/ja043534z


Related references

An efficient and general method for the synthesis of alpha,omega-difunctional reduced polypropionates by Zr-catalyzed asymmetric carboalumination: synthesis of the scyphostatin side chain. Angewandte Chemie 43(22): 2911-2914, 2004

Highly efficient asymmetric synthesis of fluvirucinine A1 via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA)-lipase-catalyzed acetylation tandem process. Organic Letters 10(2): 193-195, 2007

Efficient and selective synthesis of siphonarienolone and related reduced polypropionates via Zr-catalyzed asymmetric carboalumination. Organic Letters 6(9): 1425-1427, 2004

Efficient and selective synthesis of 6,7-Dehydrostipiamide via Zr-catalyzed asymmetric carboalumination and Pd-catalyzed cross-coupling of organozincs. Organic Letters 6(19): 3245-3248, 2004

Efficient and stereoselective synthesis of yellow scale pheromone via alkyne haloboration, Zr-catalyzed asymmetric carboalumination of alkenes (ZACA reaction), and Pd-catalyzed tandem Negishi coupling. Organic Letters 10(19): 4311-4314, 2008

Highly enantioselective synthesis of γ-, δ-, and ε-chiral 1-alkanols via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA)-Cu- or Pd-catalyzed cross-coupling. Proceedings of the National Academy of Sciences of the United States of America 111(23): 8368-8373, 2014

Catalytic asymmetric epoxidation of alpha,beta-unsaturated amides: efficient synthesis of beta-aryl alpha-hydroxy amides using a one-pot tandem catalytic asymmetric epoxidation-Pd-catalyzed epoxide opening process. Journal of the American Chemical Society 124(49): 14544-5, 2002

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. Chemistry, An Asian Journal 8(8): 1829-1835, 2014

An efficient and general route to reduced polypropionates via Zr-catalyzed asymmetric CC bond formation. Proceedings of the National Academy of Sciences of the United States of America 101(16): 5782-5787, 2004

Catalytic, efficient, and syn-selective construction of deoxypolypropionates and other chiral compounds via Zr-catalyzed asymmetric carboalumination of allyl alcohol. Journal of the American Chemical Society 128(9): 2770-2771, 2006

Catalytic asymmetric induction of planar chirality by palladium-catalyzed asymmetric cross-coupling of a meso chromium complex. Tetrahedron Letters 34(1): 107-110, 1993

Fully reagent-controlled asymmetric synthesis of (-)-spongidepsin via the Zr-catalyzed asymmetric carboalumination of alkenes (ZACA reaction). Organic Letters 9(15): 2771-2774, 2007

Efficient and selective synthesis of (S,R,R,S,R,S)-4,6,8,10,16,18-hexamethyl-docosane via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA reaction). Organic Letters 10(6): 1099-1101, 2008

A convenient and asymmetric protocol for the synthesis of natural products containing chiral alkyl chains via Zr-catalyzed asymmetric carboalumination of alkenes. Synthesis of phytol and vitamins E and K. Organic Letters 3(21): 3253-3256, 2001

Catalytic asymmetric synthesis of complex polypropionates: Lewis base catalyzed aldol equivalents in the synthesis of erythronolide B. Angewandte Chemie 49(14): 2591-2594, 2010