Enantioselective Catalysis Coupled with Stereodivergent Cyclization Strategies Enables Rapid Syntheses of (+)-Limaspermidine and (+)-Kopsihainanine A.

نویسندگان

  • Beau P Pritchett
  • Etienne J Donckele
  • Brian M Stoltz
چکیده

Enantioselective Pd-catalyzed allylic alkylations of dihydropyrido[1,2-a]indolone (DHPI) substrates were used to construct the C20-quaternary stereocenters of multiple monoterpene indole alkaloids. Stereodivergent Pictet-Spengler and Bischler-Napieralski cyclization/reduction cascades furnish the cis- and trans-fused azadecalin subunits present in Aspidosperma and Kopsia alkaloids, respectively, en route to highly efficient syntheses of (+)-limaspermidine and (+)-kopsihainanine A.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Enantioselective Cascade Cyclization/Protodemetalation of Polyenes with N3Pt2+ Catalysts

The combination of the N-based pincer ligand PyBOX with Pt2+ leads to new catalysts for the enantioselective cycloisomerization of dienyl- and trienyl-ols. The mechanistic combination of electrophilic cyclization followed by rapid protodemetalation is surprising and leads to a powerful construct for developing new reactions.

متن کامل

Enantioselective copper-catalyzed construction of aryl pyrroloindolines via an arylation-cyclization cascade.

An enantioselective arylation-cyclization cascade has been accomplished using a combination of diaryliodonium salts and asymmetric copper catalysis. These mild catalytic conditions provide a new strategy for the enantioselective construction of pyrroloindolines, an important alkaloid structural motif that is commonly found among biologically active natural products.

متن کامل

Enantioselective syntheses of pachastrissamine and jaspine A via hydroxylactonization of a chiral epoxy ester.

A new enantioselective total synthesis of pachastrissamine (jaspine B) was achieved from a known alpha,beta-unsaturated aldehyde by utilizing Córdova's asymmetric epoxidation as the chirality-inducing step. The 2,3-cis stereochemistry of pachastrissamine was established via intramolecular epoxide ring opening of a gamma,delta-epoxy-alpha,beta-unsaturated ester intermediate coupled with oxy-Mich...

متن کامل

Enantioselective Prins cyclization: BINOL-derived phosphoric acid and CuCl synergistic catalysis.

The first catalytic enantioselective Prins cyclization is disclosed. The reaction is catalyzed by the combination of a chiral BINOL-derived bis-phosphoric acid and CuCl. The process consists of a tandem Prins/Friedel-Crafts cyclization that affords the hexahydro-1H-benzo[f]isochromenes products with three new contiguous stereogenic centers in high yields, and good enantio- and excellent diaster...

متن کامل

Total synthesis of (+)-kopsihainanine A.

Total synthesis of (+)-kopsihainanine A was accomplished on the basis of (i) Stoltz's enantioselective decarboxylative asymmetric allylation and (ii) the proposed biogenetic pathway from the related alkaloid, kopsihainanine B. In addition, HPLC analysis of the synthetic (+)-kopsihainanine A confirmed its ee to be 99% with [α] = 25.35.

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Angewandte Chemie

دوره 56 41  شماره 

صفحات  -

تاریخ انتشار 2017