94233-73-5

Upstream product

• 24850-33-7 allyltributylstanane 
• 79026-61-2 (R)-3-benzyloxy-2-methylpropanal 
• 762-72-1 allyl-trimethyl-silane 
• 56850-58-9 methyl (2R)-3-(benzyloxy)-2-methylpropanoate 
• 63930-46-1 (S)-3-benzyloxy-2-methylpropan-1-ol 
• 89046-67-3 (5R)-6-benzyloxy-5-methyl-4-hydroxyhex-1-ene 
• 94233-74-6 (2R,3S)-1-(benzyloxy)-2-methylhex-5-en-3-ol 
• 197771-01-0 (5R,4R)-6-benzyloxy-5-methyl-4-(4-nitrobenzoyloxy)hex-1-ene 

Downstream Products

• 149083-09-0 Malonic acid (R)-1-((R)-2-benzyloxy-1-methyl-ethyl)-but-3-enyl ester methyl ester 
• 947412-05-7 C₂₂H₂₈O₄ 
• 947412-06-8 C₂₆H₃₄O₅ 
• 947412-07-9 C₁₈H₂₆O₄ 
• 947412-02-4 C₂₁H₂₃NO₆ 
• 947412-04-6 C₂₂H₂₈O₃ 
• 135708-79-1 (2R,3S,5S,6R)-1-Benzyloxy-2,6-dimethyl-oct-7-ene-3,5-diol 
• 135708-79-1 (2R,3R,5S,6R)-1-Benzyloxy-2,6-dimethyl-oct-7-ene-3,5-diol 
• 135708-89-3 (3R,4S,6S,7R)-8-Benzyloxy-2-((1S,4R,5R)-4-benzyloxy-5-methoxy-cyclohex-2-enyl)-4,6-bis-(tert-butyl-dimethyl-silanyloxy)-3,7-dimethyl-octanoic acid 1,3-dioxo-1,3-dihydro-isoindol-2-yl ester 
• 135708-85-9 C₄₉H₈₄O₇Si₃ 
• 135708-86-0 C₄₉H₈₄O₇Si₃ 
• 135708-84-8 (3R,4S,6S,7R)-8-Benzyloxy-4,6-bis-(tert-butyl-dimethyl-silanyloxy)-3,7-dimethyl-octanoic acid (1S,5R,6S)-6-benzyloxy-5-methoxy-cyclohex-2-enyl ester 
• 135708-87-1 (3R,4S,6S,7R)-8-Benzyloxy-2-((1S,4R,5R)-4-benzyloxy-5-methoxy-cyclohex-2-enyl)-4,6-bis-(tert-butyl-dimethyl-silanyloxy)-3,7-dimethyl-octanoic acid 
• 135708-90-6 C₄₂H₇₀O₅Si₂ 

Relevant academic research and scientific papers

[2,3]Wittig rearrangement of enantiomerically-defined α-(allyloxy)stannanes: Solid evidence for inversion of configuration at the lithium-bearing migrating terminus

The [2,3]Wittig rearrangement of enantiomerically-defined α-(allyloxy)stannanes, prepared from (S)-1-tributylstannyl-1-propanol, with butyllithium is shown to proceed with essentially complete inversion of configuration at the lithium-bearing migrating terminus. This inversion stereochemistry is further confirmed by the rearrangement of diastereomerically-defined α-(allyloxy)stannanes.

Total Synthesis and Stereochemical Revision of Stereocalpin A: Mirror-Image Approach for Stereochemical Assignments of the Peptide-Polyketide Macrocycle

Stereocalpin A is a cyclic depsipeptide with cytotoxic activity isolated from the Antarctic lichen Stereocaulon alpinum. Although a number of synthetic investigations of the unprecedented 12-membered macrocycle of stereocalpin A with a dipeptide segment and a polyketide substructure have been conducted, the configurational assignment has not been completed. In this study, we achieved the first total synthesis and stereochemical revision of stereocalpin A. To facilitate the comprehensive assessment of eight possible stereocalpin A isomers, four stereoisomers of polyketide precursors were conjugated with l-Phe-l-MePhe and d-Phe-d-MePhe dipeptides (MePhe: N-methylphenylalanine) to provide four possible isomers and four mirror-image structures of the remaining isomers, respectively. The comparative NMR analysis of a series of stereoisomers revealed that stereocalpin A possesses 2R,4S,5R-configurations, which is unique among the related 12-membered hybrid peptide-polyketide natural products reported recently. The NOE correlations in the polyketide substructure of stereocalpin A were also retrospectively analyzed among the eight possible stereoisomers.

Studies on the synthesis of bitungolides A-E: Synthesis of the C(1-C(12) fragment

Synthesis of the core segment of bitungolides A-E has been achieved in 17 steps and 4.7% overall yield. Six stereogenic centers of bitungolides A-E were established via allylation, dihydroxylation, Myers alkylation, and Evans aldol reaction Thieme Stuttgart.

Synthetic studies on a marine natural product, palmerolide A: Synthesis of C1-C9 and C15-C21 fragments

An efficient cross metathesis and Pd-catalyzed allylic rearrangement have been successfully used to construct the northern hemisphere of a cytotoxic marine natural product, palmerolide A. Georg Thieme Verlag Stuttgart.

Stereoselective synthesis of the C1-C10 fragment of rhizoxin D

A novel approach towards the synthesis of the C1-C10 fragment of the biologically active antimitotic agent rhizoxin D is described. The synthesis involves a stereoselective Michael addition reaction of lithium diallyl cuprate with an α,β-unsaturated six m

Total synthesis of rhizoxin D, a potent antimitotic agent from the fungus Rhizopus chinensis

Rhizoxin D (2) was synthesized from four subunits, A, B, C, and D representing C3-C9, C10-C13, C14-C19, and C20-C27, respectively. Subunit A was prepared by cyclization of iodo acetal 21, which set the configuration at C5 of 2 through a stereoselective addition of the radical derived from dehalogenation of 21 at the β carbon of the (Z)-α,β-unsaturated ester. Aldehyde 29 was obtained from phenylthioacetal 24 and condensed with phosphorane 30, representing subunit B, in a Wittig reaction that gave the (E,E)-dienoate 31. This ester was converted to aldehyde 33 in preparation for coupling with subunit C. The latter in the form of methyl ketone 55 was obtained in six steps from propargyl alcohol. An aldol reaction of 33 with the enolate of 55 prepared with (+)-DIPCl gave the desired β-hydroxy ketone 56 bearing a (13S)-configuration in a 17-20:1 ratio with its (13R)-diastereomer. After reduction to anti diol 57 and selective protection as TIPS ether 58, the C15 hydroxyl was esterified to give phosphonate 59. An intramolecular Wadsworth-Emmons reaction of aldehyde 62, derived from δ-lactone 60, furnished macrolactone 63, which was coupled in a Stille reaction with stannane 68 to give 2 after cleavage of the TIPS ether.

Synthetic studies toward ansatrienines: Application of the Evans- Tishchenko reaction to chiral enones

Practical syntheses of the C9-C14 sterotriade 5 and the C1-C8 polyene unit 6 in ansatrienine A (mycotriene) (1a), and other ansamycin antibiotics is described. A key step for controlling the configuration of the stereogenic center at C13 involves the stereoselective reduction of enone 10 using the Evans-Tishchenko reaction.

Studies on the total synthesis of the macrolide antitumor agent rhizoxin. 1. Synthesis of the C3-C13 segment

An asymmetric synthesis of the C3-C13 segment of rhizoxin is described in which the relative stereochemistry of C7 and C8 is established through a chelation-controlled allylation followed by Mitsunobu inversion, and the pyran ring is constructed by a phot

Synthetic Studies on the Rhizoxins. 1. Two Stereoselective Routes to a Functionalized C1-C9 Subunit

Two syntheses of a potential C1-C9 subunit of rhizoxin are described.In the first, chelation-controlled allylstannane addition to optically pure aldehyde 3, conversion to unsaturated ester 7, and stereoselective intramolecular Michael addition is used to

ACYCLIC STEREOSELECTION. 20. HIGH DIASTEREOFACIAL SELECTIVITY IN THE STANNIC CHLORIDE MEDIATED REACTIONS OF ALLYLSILANES WITH CHIRAL α- AND β-ALKOXY ALDEHYDES.

Stannic chloride is an effective catalyst for the reaction of allylsilanes with chiral α- and β-alkoxy aldehydes.In the case of α-alkoxy aldehyde 1, the diastereofacial preference is outstanding (>35:1).With β-alkoxy aldehydes 5 and 6, selectivity lower, but still quite acceptable (7-12:1).