Diastereoselective synthesis of trisubstituted olefins using a silicon-tether ring-closing metathesis strategy

Abstract: A retrosynthetic disconnection-reconnection analysis of epoxypolyenes – substrates that can undergo cyclization to podocarpane-type tricycles – reveals relay-actuated Δ6,7-functionalized monoterpenoid alcohols for ruthenium benzylidene catalyzed olefin cross metathesis with homoprenyl benzenes. Successful implementation of this approach provided several epoxypolyenes as expected (E:Z, ca. 2-3:1). The method is further generalized for the cross metathesis of pre-existing trisubstituted olefins in other relay-actuated Δ6,7-functionalized monoterpenoid alcohols with various other trisubstituted alkenes to form new trisubstituted olefins. Epoxypolyene cyclization of an enantiomerically pure, but geometrically impure, epoxypolyene substrate provides an enantiomerically pure, trans-fused, podocarpane-type tricycle (from the E-geometrical isomer).

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Copper-Catalyzed Hydroarylation of Internal Alkynes: Highly Regio- and Diastereoselective Synthesis of 1,1-Diaryl, Trisubstituted Olefins

ACS Catalysis ◽

10.1021/acscatal.7b01847 ◽

2017 ◽

Vol 7 (9) ◽

pp. 6220-6224 ◽

Cited By ~ 19

Author(s):

Gregory D. Kortman ◽

Kami L. Hull

Keyword(s):

Diastereoselective Synthesis ◽

Internal Alkynes ◽

Trisubstituted Olefins

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A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids for Cross-Metathesis with Trisubstituted Alkenes

The Journal of Organic Chemistry ◽

10.1021/acs.joc.0c00067 ◽

2020 ◽

Vol 85 (7) ◽

pp. 4906-4917 ◽

Cited By ~ 1

Author(s):

Karim A. Bahou ◽

D. Christopher Braddock ◽

Adam G. Meyer ◽

G. Paul Savage ◽

Zhensheng Shi ◽

...

Keyword(s):

Cross Metathesis ◽

Trisubstituted Olefins ◽

Trisubstituted Alkenes

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ChemInform Abstract: Diastereoselective Synthesis of P-Stereogenic Heterocycles via Enyne Ring-Closing Metathesis.

ChemInform ◽

10.1002/chin.201031189 ◽

2010 ◽

Vol 41 (31) ◽

pp. no-no

Author(s):

James Stephen Harvey ◽

Guy T. Giuffredi ◽

Veronique Gouverneur

Keyword(s):

Diastereoselective Synthesis ◽

Ring Closing Metathesis

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Enantio- and Diastereoselective Synthesis of Cyclic β-Hydroxy Allylsilanes via Sequential Aldehyde γ-Silylallylboration and Ring-Closing Metathesis Reactions

Organic Letters ◽

10.1021/ol034347t ◽

2003 ◽

Vol 5 (10) ◽

pp. 1693-1696 ◽

Cited By ~ 32

Author(s):

Jung-Nyoung Heo ◽

Glenn C. Micalizio ◽

William R. Roush

Keyword(s):

Diastereoselective Synthesis ◽

Ring Closing Metathesis ◽

Metathesis Reactions

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Diastereoselective synthesis of trisubstituted olefins using a silicon-tether ring-closing metathesis strategy

An Enantio- and Diastereoselective Synthesis of Fluorinated β-Aminoalkyl­oxepine Derivatives through Mannich and Ring-Closing Metathesis Reactions

Diastereoselective Synthesis of Fluorinated, Seven-Membered β-Amino Acid Derivatives via Ring-Closing Metathesis.

Enantio- and Diastereoselective Synthesis of Cyclic β-Hydroxy Allylsilanes via Sequential Aldehyde γ-Silylallylboration and Ring-Closing Metathesis Reactions.

Diastereoselective Synthesis of trans -2,3-Diaryl(heteroaryl)-3,6-dihydropyrans by an Allylboration/Ring-Closing-Metathesis Sequence

Diastereoselective Synthesis of P-Stereogenic Heterocycles via Enyne Ring-Closing Metathesis

A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids to Form New Trisubstituted Olefins by Cross Metathesis

Copper-Catalyzed Hydroarylation of Internal Alkynes: Highly Regio- and Diastereoselective Synthesis of 1,1-Diaryl, Trisubstituted Olefins

A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids for Cross-Metathesis with Trisubstituted Alkenes

ChemInform Abstract: Diastereoselective Synthesis of P-Stereogenic Heterocycles via Enyne Ring-Closing Metathesis.

Enantio- and Diastereoselective Synthesis of Cyclic β-Hydroxy Allylsilanes via Sequential Aldehyde γ-Silylallylboration and Ring-Closing Metathesis Reactions

An Enantio- and Diastereoselective Synthesis of Fluorinated β-Aminoalkyloxepine Derivatives through Mannich and Ring-Closing Metathesis Reactions