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. 2021 Jul 2;86(13):9233-9243.
doi: 10.1021/acs.joc.1c00872. Epub 2021 Jun 15.

Tethered Silanoxyiodination of Alkenes

Ranjeet A Dhokale  1 , Frederick J Seidl  2 , Anand H Shinde  1 , Joel T Mague  3 , Shyam Sathyamoorthi  1
Affiliations

Tethered Silanoxyiodination of Alkenes

Ranjeet A Dhokale et al. J Org Chem. .

Abstract

We present the first examples of tethered silanoxyiodination reactions of allylic alcohols. The products are useful silanediol organoiodide synthons and are formed with high regioselectivity and diastereocontrol. The reaction is scalable greater than 10-fold without loss of yield or selectivity. Furthermore, the products are starting materials for further transformations, including deiodination, C-N bond installation, epoxide synthesis, and desilylation. DFT calculations provide a basis for understanding the exquisite 6-endo selectivity of this silanoxyiodination reaction and show that the observed products are both kinetically and thermodynamically preferred.

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Figures

Figure 1.
Figure 1.
DFT energies for cationic iodonium rearrangements of substrate 1.
Scheme 1.
Scheme 1.
Organoiodides have proven versatility.
Scheme 2.
Scheme 2.
Elegant work with iodolactonization and iodoetherification inspired this tethered silanoxyiodination.
Scheme 3.
Scheme 3.
Substrate Scope.
Scheme 3.
Scheme 3.
Substrate Scope.
Scheme 4.
Scheme 4.
Silanoxyiodination scales greater than ten fold without loss of yield or selectivity.
Scheme 5.
Scheme 5.
Products are versatile synthons for: (A) de-iodination (B) C-N bond formation (C) epoxide formation and (D) silicon removal.
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