96203-70-2

Usage

InChI:InChI=1/C14H15NO8/c16-8-5-3-1-4-13(23-2-22-4)9(17)6(3)14(21)15-7(5)10(18)12(20)11(8)19/h1,5,7-8,10-12,16-20H,2H2,(H,15,21)/t5-,7-,8-,10+,11+,12+/m1/s1

Upstream product

• 120882-41-9 N,N-Diethyl-4-<(tert-butyldimethylsilyl)oxy>-6-(1,3-butadienyl)-1,3-benzodioxole-5-carboxamide 
• 87-66-1 2-hydroxyresorcinol 
• 1193340-99-6 (1R,2S,3S,4S,4aR,11bR)-2,7-dibenzyloxy-1,3,4-trihydroxy-1,3,4,4a,5,11b-hexahydro-2H-[1,3]dioxolo[4,5-j]phenanthridin-6-one 
• 83603-30-9 (1R,2S,3S,4S,4aR,11bR)-1,3,4,4a,5,11b-Hexahydro-1,2,3,4-tetrahydroxy<1,3>dioxolo<4,5-j>phenanthridin-6(2H)-on 
• 17680-04-5 (3,4-methylenedioxy)phenylmagnesium bromide 
• 71-43-2 benzene 
• 130669-75-9 (3aS,7aS)-4-bromo-2,2-dimethyl-3a,7a-dihydro-1,3-benzodioxole 
• 67451-62-1 cis-(1S,2S)-1,2-dihydroxy-3-bromocyclohexa-3,5-diene 
• 220046-09-3 [(1R,2R,6S)-6-Hydroxy-2-(7-methoxy-benzo[1,3]dioxol-5-yl)-5-oxo-cyclohex-3-enyl]-carbamic acid methyl ester 
• 208193-04-8 3-Chloro-benzoic acid (1R,2R,3R)-3-(7-methoxy-benzo[1,3]dioxol-5-yl)-2-methoxycarbonylamino-6-oxo-cyclohexyl ester 
• 208193-05-9 3-Chloro-benzoic acid (1S,2R,3R)-3-(7-methoxy-benzo[1,3]dioxol-5-yl)-2-methoxycarbonylamino-6-oxo-cyclohexyl ester 
• 208193-02-6 [(1R,6R)-6-(7-Methoxy-benzo[1,3]dioxol-5-yl)-3-triisopropylsilanyloxy-cyclohex-2-enyl]-carbamic acid methyl ester 
• 208193-07-1 C₃₂H₃₄ClNO₈SeSi 
• 208193-12-8 Acetic acid (1R,2S,3S,4S,5R,6R)-2,3,4-triacetoxy-6-(7-methoxy-benzo[1,3]dioxol-5-yl)-5-methoxycarbonylamino-cyclohexyl ester 

Downstream Products

• 28233-43-4 4,7-dihydroxy-[1,3]dioxolo[4,5-j]phenanthridin-6(5H)-one 

Relevant academic research and scientific papers

A concise synthesis of (+)-pancratistatin using pinitol as a chiral building block

A concise approach toward (+)-Pancratistatin has been achieved via 12 steps from pinitol. An ultrasound assisted arylcerium induced ring opening of cyclic sulfate was employed as a key step.

Synthesis of (+)-Pancratistatins via Catalytic Desymmetrization of Benzene

A concise synthesis of (+)-pancratistatin and (+)-7-deoxypancratistatin from benzene using an enantioselective, dearomative carboamination strategy has been achieved. This approach, in combination with the judicious choice of subsequent olefin-type difunctionalization reactions, permits rapid and controlled access to a hexasubstituted core. Finally, minimal use of intermediary steps as well as direct, late stage C-7 hydroxylation provides both natural products in six and seven operations.

ISOCARBOSTYRIL ALKALOIDS AND FUNCTIONALIZATION THEREOF

Enantioselective total syntheses of the anticancer isocarbostyril alkaloids (+)-7-deoxypancratistatin, (+)-pancratistatin, (+)-lycoricidine, and (+)-narciclasine are described. Our strategy for accessing this unique class of natural products is based on the development of a Ni-catalyzed dearomative trans-1,2-carboamination of benzene. The effectiveness of this dearomatization approach is notable, as only two additional olefin functionalizations are needed to construct the fully decorated aminocyclitol cores of these alkaloids. Installation of the lactam ring has been achieved through several pathways and a direct interconversion between natural products was established via a late-stage C-7 cupration. Using this synthetic blueprint, we were able to produce natural products on a gram scale and provide tailored analogs with improved activity, solubility, and metabolic stability.

Enantioselective Synthesis of Isocarbostyril Alkaloids and Analogs Using Catalytic Dearomative Functionalization of Benzene

Enantioselective total syntheses of the anticancer isocarbostyril alkaloids (+)-7-deoxypancratistatin, (+)-pancratistatin, (+)-lycoricidine, and (+)-narciclasine are described. Our strategy for accessing this unique class of natural products is based on the development of a Ni-catalyzed dearomative trans-1,2-carboamination of benzene. The effectiveness of this dearomatization approach is notable, as only two additional olefin functionalizations are needed to construct the fully decorated aminocyclitol cores of these alkaloids. Installation of the lactam ring has been achieved through several pathways and a direct interconversion between natural products was established via a late-stage C-7 cupration. Using this synthetic blueprint, we were able to produce natural products on a gram scale and provide tailored analogs with improved activity, solubility, and metabolic stability.

METAL CATALYZED DEAROMATIVE 1,2-CARBOAMINATION

Described herein is the development of an arenophile-mediated, nickel-catalyzed dearomative trans-1,2-carboamination protocol. A range of readily available aromatic compounds was converted to the corresponding dienes using Grignard reagents as nucleophiles. This strategy provided products with exclusive trans-selectivity and high enantioselectivity was observed in case of benzene and naphthalene. The utility of this methodology was showcased by controlled and stereoselective preparation of small, functionalized molecules. A concise synthesis of (+)-pancratistatin and (+)-7-deoxypancratistatin from benzene using an enantioselective, dearomative carboamination strategy has been achieved. This approach, in combination with the judicious choice of subsequent olefin-type difunctionalization reactions, permits rapid and controlled access to a hexasubstituted core. Finally, minimal use of intermediary steps as well as direct, late stage C-7 hydroxylation provides both natural products in six and seven operations.

Total Synthesis of (+)-Pancratistatin by the Rh(III)-Catalyzed Addition of a Densely Functionalized Benzamide to a Sugar-Derived Nitroalkene

Herein, we report the concise total synthesis of (+)-pancratistatin, accessed in a 10-step linear sequence from commercially available inputs. The convergent synthesis features a highly diastereoselective Rh(III)-catalyzed C-H bond addition to a d-glucose

Enantioselective synthesis of protected nitrocyclohexitols with five stereocenters. Total synthesis of (+)-pancratistatin

2-Methoxymethylpyrrolidine best performed, among several other proline derivatives, to control the enantioselective [3+3] annulation of β-(hetero)aryl-α-nitro-α,β-enals with commercial 2,2-dimethyl-1,3-dioxan-5-one, a procedure that renders highly oxygenated nitrocyclohexanes endowed with five new stereocenters. Use of this reaction allowed the development of a total synthesis of the antitumoral natural product (+)-pancratistatin; it also converted our previous racemic route to tetrodotoxin into an enantioselective one.

β-silyl styrene as a dienophile in the cycloaddition with 3,5-dibromo-2-pyrone for the total synthesis of (±)-pancratistatin

A new synthetic route to (±)-pancratistatin was devised utilizing β-silyl styrene as a dienophile in the cycloaddition with 3,5-dibromo-2-pyrone. The TMS group incorporated in the cycloadduct permitted a facile elimination process for the eventual install

Convergent synthesis of pancratistatin from piperonal and xylose

A synthesis of the antitumour agent pancratistatin is described from piperonal and D-xylose. Piperonal is converted into cinnamyl bromide 11 while methyl 5-iodoribofuranoside 12 is derived from xylose, The allylic bromide and the iodocarbohydrate are combined in a zinc-mediated tandem reaction to afford a highly functionalised 1,7-diene, which is then converted into the corresponding cyclohexene by ring-closing olefin metathesis. Subsequent Overman rearrangement, dihydroxylation and deprotection afford the natural product in a total of 25 steps from, the two starting materials. The longest linear sequence is from piperonal and gives rise to pancratistatin in 18 steps and 7.0% overall yield. Wiley-VCH Verlag GmbH & Co. KGaA.

PROCESSES FOR THE PREPARATION OF PANCRATISTATIN AND PANCRATISTATIN ANALOGUES

Processes for the preparation of pancratistatin and pancratistatin analogues. The key step is the reaction of a 1,3-dioxan-5-one and a nitroolefine in the presence of an amine. The process may take place in an enantioselective way when a chiral amine is u