TY - JOUR

T1 - Alkynes as synthetic equivalents of ketones and aldehydes

T2 - A hidden entry into carbonyl chemistry

AU - Alabugin, Igor V.

AU - Gonzalez-Rodriguez, Edgar

AU - Kawade, Rahul Kisan

AU - Stepanov, Aleksandr A.

AU - Vasilevsky, Sergei F.

N1 - Publisher Copyright: © 2019 by the authors. Copyright: Copyright 2019 Elsevier B.V., All rights reserved.

PY - 2019/3/15

Y1 - 2019/3/15

N2 - The high energy packed in alkyne functional group makes alkyne reactions highly thermodynamically favorable and generally irreversible. Furthermore, the presence of two orthogonal π-bonds that can be manipulated separately enables flexible synthetic cascades stemming from alkynes. Behind these “obvious” traits, there are other more subtle, often concealed aspects of this functional group’s appeal. This review is focused on yet another interesting but underappreciated alkyne feature: the fact that the CC alkyne unit has the same oxidation state as the -CH2C(O)- unit of a typical carbonyl compound. Thus, “classic carbonyl chemistry” can be accessed through alkynes, and new transformations can be engineered by unmasking the hidden carbonyl nature of alkynes. The goal of this review is to illustrate the advantages of using alkynes as an entry point to carbonyl reactions while highlighting reports from the literature where, sometimes without full appreciation, the concept of using alkynes as a hidden entry into carbonyl chemistry has been applied.

AB - The high energy packed in alkyne functional group makes alkyne reactions highly thermodynamically favorable and generally irreversible. Furthermore, the presence of two orthogonal π-bonds that can be manipulated separately enables flexible synthetic cascades stemming from alkynes. Behind these “obvious” traits, there are other more subtle, often concealed aspects of this functional group’s appeal. This review is focused on yet another interesting but underappreciated alkyne feature: the fact that the CC alkyne unit has the same oxidation state as the -CH2C(O)- unit of a typical carbonyl compound. Thus, “classic carbonyl chemistry” can be accessed through alkynes, and new transformations can be engineered by unmasking the hidden carbonyl nature of alkynes. The goal of this review is to illustrate the advantages of using alkynes as an entry point to carbonyl reactions while highlighting reports from the literature where, sometimes without full appreciation, the concept of using alkynes as a hidden entry into carbonyl chemistry has been applied.

KW - Acetals

KW - Aldehydes

KW - Alkynes

KW - Carbonyl compounds

KW - Catalysis

KW - Condensations

KW - Cyclizations

KW - Electronic structure

KW - Ketones

KW - Nucleophilic addition

KW - Rearrangements

KW - acetals

KW - ANNULATIVE PI-EXTENSION

KW - alkynes

KW - BAEYER-VILLIGER OXIDATION

KW - condensations

KW - catalysis

KW - ketones

KW - cyclizations

KW - aldehydes

KW - STEREOELECTRONIC CONTROL

KW - electronic structure

KW - COUPLING REACTION

KW - GRAPHENE NANORIBBONS

KW - carbonyl compounds

KW - BALDWIN RULES

KW - C-NUCLEOSIDE SYNTHESIS

KW - rearrangements

KW - GOLD-CATALYZED CYCLOISOMERIZATION

KW - 6-ENDO-DIG CYCLIZATIONS

KW - nucleophilic addition

KW - RING-CLOSURE

UR - http://www.scopus.com/inward/record.url?scp=85062970593&partnerID=8YFLogxK

U2 - 10.3390/molecules24061036

DO - 10.3390/molecules24061036

M3 - Article

C2 - 30875972

AN - SCOPUS:85062970593

VL - 24

JO - Molecules

JF - Molecules

SN - 1420-3049

IS - 6

M1 - 1036

ER -