Toward the stereochemical assignment and synthesis of hemicalide: DP4f GIAO-NMR analysis and synthesis of a reassigned C16-C28 subunit.

نویسندگان

  • Callum I MacGregor
  • Bing Yuan Han
  • Jonathan M Goodman
  • Ian Paterson
چکیده

Using the DP4f GIAO-NMR method, the stereochemistry of hemicalide was computationally analysed, resulting in a reassignment at C18 as supported by improved NMR shift correlations with a model C13-C25 fragment 23. An advanced C16-C28 subunit 6 of this potent anticancer agent was then synthesised with the revised 18,19-syn relationship.

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

A synthesis-enabled relative stereochemical assignment of the C1-C28 region of hemicalide.

Through synthesising both candidate diastereomers of a model C1-C28 fragment of the potent cytotoxic marine polyketide hemicalide, an assignment of the relative configuration between the C1-C15 and C16-C26 regions has been achieved. By detailed NMR comparisons with the natural product, the relative stereochemistry between these two 1,6-related stereoclusters is elucidated as 13,18-syn rather th...

متن کامل

Computational study in Regioselectivie Synthesis of New Spiro-oxindolopyrrolidines

One-pot, four-component procedure for the synthesis of a small library of new chiral spiro- oxindolopyrrolidines with high regio-, diastereo- (>99:1 dr), and enantioselectivity (up to 80% ee) is described. In this process, the regio- and stereochemical 1,3-dipolar cycloaddition of azomethine ylides, which were generated insitu by the reaction of isatin derivatives and sarcosin,with optically ac...

متن کامل

Computational study in Regioselectivie Synthesis of New Spiro-oxindolopyrrolidines

One-pot, four-component procedure for the synthesis of a small library of new chiral spiro- oxindolopyrrolidines with high regio-, diastereo- (>99:1 dr), and enantioselectivity (up to 80% ee) is described. In this process, the regio- and stereochemical 1,3-dipolar cycloaddition of azomethine ylides, which were generated insitu by the reaction of isatin derivatives and sarcosin,with optically ac...

متن کامل

Synthesis and Stereochemical Assignment of (+)-Chamuvarinin

A stereocontrolled total synthesis of (+)-chamuvarinin, isolated from the root extract of Uvaria Chamae, utilizes a convergent modular strategy to construct the adjacently linked C15-C28 ether array, followed by a late-stage Julia-Kocienski olefination to append the butenolide motif. This constitutes the first total synthesis of (+)-chamuvarinin, defining the relative and absolute configuration...

متن کامل

Ab Initio Calculation 29Si NMR Chemical Shift Studies on Silicate Species in Aqueous and Gas Phase

Nowadays NMR spectroscopy becomes a powerful tool in chemistry because of the NMR chemical shifts. Hartree–Fock theory and the Gauge-including atomic orbital (GIAO) methods are used in the calculation of 29Si NMR chemical shifts of various silicate species in the silicate solution as initial components for zeolite synthesis both in gas and solution phase. Calculations have been performed at geo...

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:
  • Chemical communications

دوره 52 25  شماره 

صفحات  -

تاریخ انتشار 2016